Efficient Synthetic Routes to Terminal Î³-KetoâAlkynes and

Organometallics 2001, 20, 3175-3189

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Efficient Synthetic Routes to Terminal γ-Keto-Alkynes and Unsaturated Cyclic Carbene Complexes Based on Regio- and Diastereoselective Nucleophilic Additions of Enolates on Ruthenium(II) Indenyl Allenylidenes Victorio Cadierno, Salvador Conejero, M. Pilar Gamasa, and Jose´ Gimeno* Departamento de Quı´mica Orga´ nica e Inorga´ nica, Instituto Universitario de Quı´mica Organometa´ lica “Enrique Moles” (Unidad Asociada al CSIC), Facultad de Quı´mica, Universidad de Oviedo, E-33071 Oviedo, Spain

Enrique Pe´rez-Carrenõ and Santiago Garcıá-Granda Departamento de Quı´mica Fı´sica y Analı´tica, Facultad de Quı´mica, Universidad de Oviedo, E-33071 Oviedo, Spain Received March 27, 2001

Ruthenium(II) indenyl allenylidene complexes [Ru{dCdCdC(R1)Ph}(η5-C9H7)(PPh3)2][PF6] (R1 ) Ph (1), H (2)) regioselectively react with lithium enolates LiCH2COR2 (R2 ) Ph, iPr, Me, Fc, (E)-CHdCHPh) at the Cγ atom to yield the neutral σ-alkynyl derivatives [Ru{Ct CC(R1)Ph(CH2COR2)}(η5-C9H7)(PPh3)2] (3a-e, 4a-d). Protonation of 3a-e and 4a-d with HBF4‚Et2O affords the cationic vinylidene derivatives [Ru{dCdC(H)C(R1)Ph(CH2COR2)}(η5-C9H7)(PPh3)2][BF4] (5a-e, 6a-d), which can be easily demetalated, by treatment with acetonitrile, to yield the terminal γ-keto-substituted alkynes HCtCC(R1)Ph(CH2COR2) (7ae, 8a-d) and the nitrile complex [Ru(NtCMe)(η5-C9H7)(PPh3)2][BF4] (9). The addition of lithium enolates LiCH2COR (R ) Ph, iPr, Me) on the optically active allenylidene complex [Ru{dCdCdC(C9H16)}(η5-C9H7)(PPh3)2][PF6] (12; C(C9H16) ) (1R)-1,3,3-trimethylbicyclo[2.2.1]hept-2-ylidene) proceeds in a regio- and diastereoselective manner, affording σ-alkynyl derivatives [Ru{CtCC(C9H16)(CH2COR)}(η5-C9H7)(PPh3)2] (13a-c). The X-ray crystal structure of 13b shows that these enolate additions take place on the less sterically congested exo face of the allenylidene chain. Chiral alkynes HCtCC(C9H16)(CH2COR) (15a-c) have been also prepared from 13a-c via initial protonation with HBF4‚Et2O and subsequent treatment of the resulting vinylidenes 14a-c with acetonitrile. Cyclic alkenyl derivatives [Ru{CdCHC(R1)(R2)CHdC(R3)O}(η5-C9H7)(PPh3)2] (R1 ) R2 ) Ph, R3 ) Ph (18a), iPr (18b); R1R2 ) C9H16, R3 ) Ph (20)) have been obtained by treatment of dichloromethane solutions of σ-alkynyl complexes 3a,b and 13a with catalytic amounts of AlCl3 at room temperature. Protonation of these species affords the cyclic carbenes [Ru{dCCH2C(R1)(R2)CHdC(R3)O}(η5-C9H7)(PPh3)2][BF4] (19a,b, 21). Introduction As a part of the continuous interest in the chemistry of carbene complexes, allenylidene derivatives [M]dCd CdCR2 have attracted a great deal of attention in recent years due to their versatile reactivity.1 Theoretical studies clearly indicate that the CR and Cγ carbon atoms of the allenylidene chain are electrophilic centers, while the Cβ is a nucleophilic site.2 Nucleophilic attacks dominate the reactivity of allenylidene complexes, re* To whom correspondence should be addressed. E-mail: jgh@ sauron.quimica.uniovi.es. (1) For comprehensive reviews on the synthesis and reactivity of allenylidene complexes see: (a) Bruce, M. I. Chem. Rev. 1991, 91, 197. (b) Werner, H. Chem. Commun. 1997, 903. (c) Bruce, M. I. Chem. Rev. 1998, 98, 2797. (d) Touchard, D.; Dixneuf, P. H. Coord. Chem. Rev. 1998, 178-180, 409. (e) Cadierno, V.; Gamasa, M. P.; Gimeno, J. Eur. J. Inorg. Chem. 2001, 571.

vealing the great potential of these species to promote novel C-C and C-heteroatom coupling reactions.1 Moreover, it is now well-established that the regioselectivity of these nucleophilic additions is strongly dependent on the metallic fragment.1 In general, allenylidene groups attached to bulky and/or electronrich metallic fragments are unreactive toward weak nucleophiles but react with strong nucleophiles which (2) (a) Schilling, B. E. R.; Hoffman, R.; Lichtenberger, D. L. J. Am. Chem. Soc. 1979, 101, 585. (b) Berke, H.; Huttner, G.; von Seyerl, J. Z. Naturforsch. 1981, 36B, 1277. (c) Pe´rez-Carrenõ, E. Doctoral Thesis, University of Oviedo, 1996. (d) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; Modrego, J.; Onãte, E. Organometallics 1997, 16, 5826. (e) Xia, H. P.; Ng, W. S.; Ye, J. S.; Li, X.-Y.; Wong, W. T.; Lin, Z.; Yang, C.; Jia, G. Organometallics 1999, 18, 4552. (f) Re, N.; Sgamellotti, A.; Floriani, C. Organometallics 2000, 19, 1115. (g) Baya, M.; Crochet, P.; Esteruelas, M. A.; Gutie´rrez-Puebla, E.; Lo´pez, A. M.; Modrego, J.; Onãte, E.; Vela, N. Organometallics 2000, 19, 2585.

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are added regioselectively at the Cγ atom, leading to the alkynyl species [M]-CtCCR2(Nu).3 In contrast, the presence of metallic units bearing less sterically demanding and/or more π-electron-withdrawing ligands show a marked ability to add both soft and hard nucleophiles at the CR atom.4 We have described an extensive series of allenylidene complexes containing η5-indenyl-ruthenium(II) fragments and have investigated their influence on the reactivity of the cumulenic chain.3h,5 Thus, we have shown that those allenylidene groups stabilized by the electron-rich [Ru(η5-C9H7)(PPh3)2]+ moiety are able to add regioselectively a large variety of neutral and anionic nucleophiles at the Cγ atom to afford the functionalized σ-alkynyl derivatives [Ru{CtCCR1R2(Nu)}(η5-C9H7)(PPh3)2]n+ (n ) 0, 1).5c-i Furthermore, we have designed an efficient synthetic approach to terminal alkynes. They can be obtained from vinylidene (3) For representative examples see the following. [M] ) trans[RuClL2]+ (L2 ) dppm (bis(diphenylphosphino)methane), dppe (1,2bis(diphenylphosphino)ethane)): (a) Pirio, N.; Touchard, D.; Toupet, L.; Dixneuf, P. H. J. Chem. Soc., Chem. Commun. 1991, 980. (b) Touchard, D.; Pirio, N.; Dixneuf, P. H. Organometallics 1995, 14, 4920. (c) Touchard, D.; Haquette, P.; Daridor, A.; Romero, A.; Dixneuf, P. H. Organometallics 1998, 17, 3844. (d) Rigaut, S.; Maury, O.; Touchard, D.; Dixneuf, P. H. Chem. Commun. 2001, 373. [M] ) [RuCl{N(CH2CH2PPh2)3}]+: (e) Wolinska, A.; Touchard, D.; Dixneuf, P. H.; Romero, A. J. Organomet. Chem. 1991, 420, 217. [M] ) [Ru(η5-C5R5)LL′]+ (R ) H, L ) L′ ) PMe3, PPh3; R ) H, L ) PPh3, L′ ) PPh2CH2C(dO)tBu; R ) H, LL′ ) dippe (1,2-bis(diisopropylphosphino)ethane); R ) Me, L ) L′ ) PEt3; R ) Me, LL′ ) dippe): (f) Selegue, J. P. Organometallics 1982, 1, 217. (g) de los Rıós, I.; Jimeńez-Tenorio, M.; Puerta, M. C.; Valerga, P. J. Organomet. Chem. 1997, 549, 221. (h) Crochet, P.; Demerseman, B.; Vallejo, M. I.; Gamasa, M. P.; Gimeno, J.; Borge, J.; Garcıá-Granda, S. Organometallics 1997, 16, 5406. (i) Bruce, M. I.; Low, P. J.; Tiekink, E. R. T. J. Organomet. Chem. 1999, 572, 3. (j) Bustelo, E.; Jimeńez-Tenorio, M.; Puerta, M. C.; Valerga, P. Organometallics 1999, 18, 4563. [M] ) [Os(η5-C5H5)(PiPr3)2]+: see ref 2g. (4) For representative examples see the following. [M] ) M(CO)5 (M ) Cr, W): (a) Fischer, H.; Roth, G.; Reindl, D.; Troll, C. J. Organomet. Chem. 1993, 454, 133. (b) Fischer, H.; Reindl, D.; Troll, C.; Leroux, F. J. Organomet. Chem. 1995, 490, 221. (c) Fischer, H.; Roth, G. J. Organomet. Chem. 1995, 490, 229. (d) Cosset, C.; del Rio, I.; Le Bozec, H. Organometallics 1995, 14, 1938. (e) Roth, G.; Fischer, H. J. Organomet. Chem. 1996, 507, 125. (f) Cosset, C.; del Rio, I.; Pe´ron, V.; Windmu¨ller, B.; Le Bozec, H. Synlett 1996, 435. (g) Do¨tz, K. H.; Paetsch, D.; Le Bozec, H. J. Organomet. Chem. 1999, 589, 11. (h) Ulrich, K.; Porhiel, E.; Pe´ron, V.; Ferrand, V.; Le Bozec, H. J. Organomet. Chem. 2000, 601, 78. [M] ) [Mn(η5-C5H5)(CO)2]: (i) Kolobova, N. E.; Ivanov, L. L.; Zhvanko, O. S.; Khitrova, O. M.; Batsanov, A. S.; Struchkov, Y. T. J. Organomet. Chem. 1984, 265, 271. See also ref 2b. [M] ) [RuCl(η6-arene)(PR3)]+ (PR3 ) PMe3, PPh3): (j) Dussel, R.; Pilette, D.; Dixneuf, P. H. Organometallics 1991, 10, 3287. (k) Pilette, D.; Le Bozec, H.; Romero, A.; Dixneuf, P. H. J. Chem. Soc., Chem. Commun. 1992, 1220. (l) Pilette, D.; Ouzzine, K.; Dixneuf, P. H.; Rickard, C. E. F.; Roper, W. R. Organometallics 1992, 11, 809. (m) Ruiz, N.; Pe´ron, D.; Sinbandith, S.; Dixneuf, P. H.; Baldoli, C.; Maiorana, S. J. Organomet. Chem. 1997, 533, 213. See also ref 4h. [M] ) [Ru(η5-C5H5)(CO)(PR3)]+ (PR3 ) PiPr3, PPh3): (n) Esteruelas, M. A.; Go´mez, A. V.; Lahoz, F. J.; Lo´pez, A. M.; Onãte, E.; Oro, L. A. Organometallics 1996, 15, 3423. (o) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; Onãte, E.; Ruiz, N. Organometallics 1998, 17, 2297. (p) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; Onãte, E. Organometallics 1998, 17, 3567. (q) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; Puerta, M. C.; Valerga, P. Organometallics 1998, 17, 4959. (r) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; Modrego, J.; Onãte, E. Organometallics 1998, 17, 5434. (s) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; Onãte, E.; Ruiz, N. Organometallics 1999, 18, 1606. (t) Bernad, D. J.; Esteruelas, M. A.; Lo´pez, A. M.; Modrego, J.; Puerta, M. C.; Valerga, P. Organometallics 1999, 18, 4995. (u) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; Olivań, M.; Onãte, E.; Ruiz, N. Organometallics 2000, 19, 4. (v) Bernad, D. J.; Esteruelas, M. A.; Lo´pez, A. M.; Olivań, M.; Onãte, E.; Puerta, M. C.; Valerga, P. Organometallics 2000, 19, 4327. See also ref 2d and 4h. [M] ) fac,cis-[RuCl2{EtN(CH2CH2PPh2)2}]: (w) Bianchini, C.; Peruzzini, M.; Zanobini, F.; Lopez, C.; de los Rios, I.; Romerosa, A. Chem. Commun. 1999, 443. [M] ) [Re(Triphos)(CO)2]+ (Triphos ) 1,1,1-tris(diphenylphosphinomethyl)ethane): (x) Bianchini, C.; Mantovani, N.; Marchi, A.; Marvelli, L.; Masi, D.; Peruzzini, M.; Rossi, R.; Romerosa, A. Organometallics 1999, 18, 4501. (y) Bianchini, C.; Mantovani, N.; Marvelli, L.; Peruzzini, M.; Rossi, R.; Romerosa, A. J. Organomet. Chem. 2001, 617-618, 23.

Cadierno et al. Chart 1

complexes, resulting from the protonation of the functionalized σ-alkynyl complexes, followed by a demetalation process via treatment with acetonitrile.5g This procedure allows the recovery of the metallic auxiliary as the insoluble complex [Ru(NtCMe)(η5-C9H7)(PPh3)2]+, which can be separated quantitatively from the free alkynes. Chart 1 collects a number of alkynyl complexes (A-C) which can be used as efficient precursors of terminal alkynes (D-F).5g,i,6 Although these examples prove the potential synthetic utility of allenylidene complexes in organic synthesis,7 the scope of its application is still not comparable to that of the related vinylidenes [M]dCdCR2 or the classical Fischer type metal carbenes [M]dC(X)R (X ) OR′, NR′2).8-10 Pursuing these studies aimed at exploiting the utility of this synthetic route, we describe in this paper the (5) (a) Cadierno, V.; Gamasa, M. P.; Gimeno, J.; Gonza´lez-Cueva, M.; Lastra, E.; Borge, J.; Garcıá-Granda, S.; Pe´rez-Carrenõ, E. Organometallics 1996, 15, 2137. (b) Gamasa, M. P.; Gimeno, J.; Gonza´lezBernardo, C.; Borge, J.; Garcıá-Granda, S. Organometallics 1997, 16, 2483. (c) Cadierno, V.; Gamasa, M. P.; Gimeno, J.; Borge, J.; GarcıáGranda, S. Organometallics 1997, 16, 3178. (d) Cadierno, V.; Gamasa, M. P.; Gimeno, J.; Lo´pez-Gonza´lez, M. C.; Borge, J.; Garcıá-Granda, S. Organometallics 1997, 16, 4453. (e) Cadierno, V.; Gamasa, M. P.; Gimeno, J.; Pe´rez-Carrenõ, E.; Ienco, A. Organometallics 1998, 17, 5216. (f) Cadierno, V.; Conejero, S.; Gamasa, M. P.; Gimeno, J.; Asselberghs, I.; Houbrechts, S.; Clays, K.; Persoons, A.; Borge, J.; Garcıá-Granda, S. Organometallics 1999, 18, 582. (g) Cadierno, V.; Gamasa, M. P.; Gimeno, J.; Pe´rez-Carrenõ, E.; Garcıá-Granda, S. Organometallics 1999, 18, 2821. (h) Cadierno, V.; Gamasa, M. P.; Gimeno, J.; Lastra, E. J. Chem. Soc., Dalton Trans. 1999, 3235. (i) Cadierno, V.; Conejero, S.; Gamasa, M. P.; Gimeno, J. J. Chem. Soc., Dalton Trans. 2000, 451. (6) Cadierno, V.; Gamasa, M. P.; Gimeno, J. J. Organomet. Chem. 2001, 621, 39. (7) Organic cumulenes have been prepared using rhodium(I) allenylidene complexes as starting materials: (a) Wiedemann, R.; Steinert, P.; Gevert, O.; Werner, H. J. Am. Chem. Soc. 1996, 118, 2495. (b) Werner, H.; Wiedemann, R.; Mahr, N.; Steinert, P.; Wolf, J. Chem. Eur. J. 1996, 2, 561. (c) Werner, H.; Laubender, M.; Wiedemann, R.; Windmu¨ller, B. Angew. Chem., Int. Ed. Engl. 1996, 35, 1237.

Additions of Enolates on Ru(II) Indenyl Allenylidenes Chart 2

synthesis of γ-keto-substituted alkynes G and H (Chart 2). The former alkynes have been obtained by starting from the allenylidene complexes [Ru{dCdCdC(R1)Ph}(η5-C9H7)(PPh3)2][PF6] (R1 ) Ph, H) through the addition of lithium enolates LiCH2COR2. Alkynes H have been synthesized diastereoselectively using similar additions on the optically active allenylidene derivative [Ru{dCd CdC(C9H16)}(η5-C9H7)(PPh3)2][PF6] (C(C9H16) ) (1R)1,3,3-trimethylbicyclo[2.2.1]hept-2-ylidene). The preparation of unsaturated carbene complexes J, which are obtained via protonation of cyclic alkenyl derivatives I, is also reported. The alkenyl complexes I result from the intramolecular cyclization of the keto-functionalized σ-alkynyl species [Ru{CtCCR1R2(CH2COR3)}(η5-C9H7)(PPh3)2] in the presence of AlCl3. Part of this work has been communicated in a preliminary report.5e Results and Discussion Synthesis of Terminal Alkynes HCtCC(R1)Ph(CH2COR2). The synthetic route is based on the same procedure that we have previously described.5g,i Thus, with allenylidene complexes as the starting materials, the first step involves the preparation of the corresponding σ-alkynyl derivatives, which are transformed into vinylidene species. The treatment of these vinylidenes with acetonitrile finally gives the free alkynes through a demetalation process. (8) For recent reviews on the chemistry of vinylidene complexes see: (a) Werner, H. J. Organomet. Chem. 1994, 475, 44. (b) Bruneau, C.; Dixneuf, P. H. Acc. Chem. Res. 1999, 32, 311. (c) Puerta, M. C.; Valerga, P. Coord. Chem. Rev. 1999, 193-195, 977. See also ref 1a. (9) Extensive surveys and reviews have been published on the chemistry of Fischer type carbene complexes. For recent references see: (a) Sierra, M. A. Chem. Rev. 2000, 100, 3591. (b) Zaragoza Do¨rwald, F. In Metal Carbenes in Organic Synthesis; Wiley-VCH: Weinheim, Germany, 1999. (c) Do¨tz, K. H.; Tomuschat, P. Chem. Soc. Rev. 1999, 28, 187. (d) Doyle, M. P.; Forbes, D. C. Chem. Rev. 1998, 98, 911. (10) A few examples of catalytic transformations of propargylic alcohols via ruthenium(II) allenylidene intermediates have been reported: (a) Trost, B. M.; Flygare, J. A. J. Am. Chem. Soc. 1992, 114, 5476. (b) Trost, B. M.; Flygare, J. A. Tetrahedron Lett. 1994, 35, 4059. (c) Nishibayashi, Y.; Wakiji, I.; Hidai, M. J. Am. Chem. Soc. 2000, 122, 11019. (d) The catalytic activity of ruthenium(II) allenylidene complexes in ring-closing metathesis (RCM) of olefins has been recently discovered: Fu¨rstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012 and references therein.

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(a) Reactions of Allenylidene Complexes [Ru{dCdCdC(R1)Ph}(η5-C9H7)(PPh3)2][PF6] with Enolates Derived from Methyl Ketones. As expected from our previous studies,5c-i the allenylidene complexes [Ru{dCdCdC(R1)Ph}(η5-C9H7)(PPh3)2][PF6] (R1 ) Ph (1), H (2))5a react with lithium enolates LiCH2COR2 (R2 ) Ph, iPr, Me, Fc, (E)-CHdCHPh) in tetrahydrofuran, at -20 °C, to afford the neutral σ-alkynyl derivatives [Ru{CtCC(R1)Ph(CH2COR2)}(η5-C9H7)(PPh3)2] (3ae, 4a-d), resulting from the regioselective addition of the nucleophile at the Cγ atom. Complexes 3a-e and 4a-d have been isolated as air-stable orange solids in 62-83% yields (Scheme 1). Analytical and spectroscopic data (IR and 1H, 31P{1H}, and 13C{1H} NMR) support the proposed formulations (see the Experimental Section and Tables 1 and 2). In particular, the formation of a γ-keto-substituted alkynyl chain was identified on the basis of (i) the presence of typical ν(CdO) and ν(CtC) absorption bands in the IR spectra (KBr) at 1652-1721 and 2052-2092 cm-1, respectively, and (ii) characteristic resonances in the 13C{1H} NMR spectra of the Ru-CtC, C , CH , and Cd γ 2 O carbon nuclei at δ 92.62-98.02 (2JCP ) 22.5-25.7 Hz, CR), 111.77-115.99 (Cβ), 37.88-50.67 (Cγ), 50.51-57.63 (CH2), and 195.68-211.21 (CdO). (b) Synthesis of Vinylidene Complexes [Ru{dCd C(H)C(R1)Ph(CH2COR2)}(η5-C9H7)(PPh3)2][BF4]. The treatment of σ-alkynyl complexes 3a-e and 4a-d with HBF4‚Et2O in diethyl ether at -20 °C generates the airstable vinylidene complexes [Ru{dCdC(H)C(R1)Ph(CH2COR2)}(η5-C9H7)(PPh3)2][BF4] (5a-e and 6a-d; 74-94% yields) (Scheme 1). Elemental analyses and spectroscopic data are in accordance with the proposed formulations (see the Experimental Section and Tables 3 and 4 for details). The most remarkable feature in the 1H NMR spectra of these complexes is the presence of a singlet (5a-e) or doublet (6a-d; ca. JHH ) 10 Hz) signal in the range 4.50-5.76 ppm attributed to the acidic vinylidene proton [Ru]dCdCH (Table 3). The characteristic deshielded CR resonance appears, in the 13C{1H} NMR spectra, as a triplet (2J CP ) 15.1-17.9 Hz) at δ 340.50-344.41, while the Cβ, Cγ, CH2 and Cd O carbon nuclei resonate as singlets at higher fields (δ 115.90-116.79 (Cβ), 34.24-48.21 (Cγ), 48.12-53.24 (CH2), and 196.89-213.36 (CdO); see Table 4). (c) Demetalation Processes. Demetalation of complexes 5a-e and 6a-d proceeds rapidly (ca. 30 min) in refluxing acetonitrile to afford terminal γ-keto-substituted alkynes HCtCC(R1)Ph(CH2COR2) (7a-e and 8ad) and the cationic nitrile complex [Ru(NtCMe)(η5C9H7)(PPh3)2][BF4] (9)5g (Scheme 1). Keto-alkynes 7a-d and 8a-d have been purified from the reaction mixture by column chromatography on silica gel (72-86% yield) after filtering off the unsoluble complex 9. They have been characterized by means of standard spectroscopic techniques and microanalysis (see the Experimental Section and Tables 5 and 6). The most relevant spectroscopic features of 7a-e and 8a-d are (i) (1H NMR) the singlet (7a-e) or doublet (8a-d; ca. JHH ) 2 Hz) resonance for the acetylenic proton (δ 2.25-2.73) and (ii) (13C{1H} NMR) typical signals for the HCtC carbons which appear in the ranges δ 70.71-75.10 and 84.8787.84, respectively.11

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Cadierno et al. Scheme 1

Table 1.

31P{1H}

and 1H NMR Data for Neutral σ-Alkynyl Complexes [Ru{CtCC(R1)Ph(CH2COR2)}(η5-C9H7)(PPh3)2]a 1H

η5-C9H7n complex

31P{1H}

H-1,3

H-2

JHH

R1 ) R2 ) Ph (3a) 53.14 s R1 ) Ph, R2 ) iPr (3b) 52.19 s

4.75 d 4.78 d

5.64 t 5.71 t

2.3 2.0

6.53 m, 6.78 m 3.99 s 6.46 m, b 3.52 s

R1 ) Ph, R2 ) Me (3c) 52.24 s R1 ) Ph, R2 ) Fc (3d) 53.42 s

4.73 d 4.70 d

5.63 t 5.63 t

2.5 2.3

6.42 m, b 3.48 s 6.56 m, 6.78 m 3.89 s

2.0

6.35 m, 6.78 m 3.72 s

R1 ) Ph, R2 ) 52.00 s 4.80 d 5.83 t (E)-CHdCHPh (3e) 1 2 R ) H, R ) Ph (4a) 52.47 br 4.54 br 5.40 br 4.71 br R1 ) H, R2 ) iPr (4b) 49.38 de 4.64 br 5.56 br 49.87 de 4.73 br R1 ) H, R2 ) Me (4c) R1 ) H, R2 ) Fc (4d)

51.88 dh 52.35 dh 51.94 dk 52.52 dk

4.67 br 5.53 br 4.73 br 4.77 br 5.59 br 4.82 br

H-4,5,6,7

CH2

6.27 m, 6.67 m 3.17 ddc 3.64 ddd 6.30 m, 6.71 m 2.76 ddf 3.04 ddg 6.35 m, 6.75 m 2.62 ddi 2.94 ddj 6.28 m, 6.69 m 3.26 ddl 3.37 ddm

others 6.84-7.76 (m, Ph) 0.91 (d, JHH ) 6.8, CH3); 2.29 (sept, JHH ) 6.8, CH); 6.81-7.63 (m, Ph) 1.85 (s, CH3); 6.81-7.57 (m, Ph) 3.81 (s, C5H5); 4.03 and 4.61 (br, C5H4); 6.87-7.89 (m, Ph) 6.52 and 7.72 (d, JHH ) 15.9, dCH); 6.89-7.60 (m, Ph) 5.04 (dd, JHH ) 9.0, JHH ) 5.3, CH); 6.84-8.03 (m, Ph) 0.91 (d, JHH ) 7.0, CH3); 0.99 (d, JHH ) 6.9, CH3); 2.36 (m, CH(CH3)2); 4.85 (dd, JHH ) 8.0, JHH ) 6.4, CH); 6.85-7.53 (m, Ph) 1.88 (s, CH3); 5.20 (dd, JHH ) 9.2, JHH ) 5.3, CH); 6.88-7.53 (m, Ph) 3.89 (s, C5H5); 4.11 and 4.60 (br, C5H4); 5.13 (dd, JHH ) 7.7, JHH ) 6.9, CH); 6.88-7.67 (m, Ph)

a Spectra recorded in C D ; δ in ppm and J in Hz. Abbreviations: s, singlet; br, broad; d, doublet; dd, doublet of doublets; t, triplet; 6 6 sept, septuplet; m, multiplet. b Overlapped by Ph protons. c JHH ) 15.5, JHH ) 5.3. d JHH ) 15.5, JHH ) 9.0. e 2JPP ) 30.3. f JHH ) 15.5, JHH ) 6.4. g JHH ) 15.5, JHH ) 8.0. h 2JPP ) 31.7. i JHH ) 14.8, JHH ) 5.3. j JHH ) 14.8, JHH ) 9.2. k 2JPP ) 29.9. l JHH ) 15.6, JHH ) 7.7. m J n HH ) 15.6, JHH ) 6.9. Legend for indenyl skeleton:

Diastereoselective Synthesis of Terminal Alkynes HCtCC(C9H16)(CH2COR). The efficient access to alkynes 7a-e and 8a-d from allenylidene complexes 1 and 2 and methyl ketones prompted us to use chiral substrates in order to obtain optically active terminal alkynes. Toward this aim, a novel allenylidene complex bearing a chiral auxiliary derived from the commercially available ketone (-)-fenchone was prepared. The subsequent transformations leading to the formation of the desired terminal alkynes are similar to those previously mentioned. (a) Synthesis of the Optically Active Allenylidene Ruthenium(II) Complex [Ru{dCdCdC(C9H16)}(η5(11) To the best of our knowledge only the terminal alkyne 8a has been previously reported: Caffyn, A. J. M.; Nicholas, K. M. J. Am. Chem. Soc. 1993, 115, 6438.

C9H7)(PPh3)2][PF6]. Following the well-known Selegue synthetic protocol,3f the chiral allenylidene derivative [Ru{dCdCdC(C9H16)}(η5-C9H7)(PPh3)2][PF6] (12) was prepared (80% yield) by refluxing [RuCl(η5-C9H7)(PPh3)2] (10),12 NaPF6, and 2-exo-ethynyl-1,3,3-trimethyl-2-endo-norbornanol (11)13 in methanol (Scheme 2). Spectroscopic data (see the Experimental Section) for 12 are similar to those reported for the related allenylidene complexes [Ru(dCdCdCRR′)(η5-C9H7)(PPh3)2][PF6].5a,h Significantly, the presence of the cumulenic moiety was clearly identified on the basis of a strong ν(CdCdC) IR absorption at 1963 cm-1 and the (12) Oro, L. A.; Ciriano, M. A.; Campo, M.; Foces-Foces, C.; Cano, F. H. J. Organomet. Chem. 1985, 289, 117. (13) Keegan, D. S.; Midland, M. M.; Werley, R. T.; McLoughlin, J. I. J. Org. Chem. 1991, 56, 1185.

Additions of Enolates on Ru(II) Indenyl Allenylidenes


Table 2. 13C{1H} NMR Data for Neutral σ-Alkynyl Complexes [Ru{CtCC(R1)Ph(CH2COR2)}(η5-C9H7)(PPh3)2]a η5-C9H7 C-3a,7a ∆δ(C-3a,7a)b C-4,5,6,7

Ru-CR

110.69

-20.01

95.42 t

96.65

110.58

-20.12

74.11

96.38

110.27

-20.43

3d

75.23

96.48

110.71

-19.99

3e

74.35

96.74

110.18

-20.52

4a

75.16e 96.38 75.38f

109.08 110.72

-20.80

4b

74.47g 95.74 74.57h

108.84 109.89

-21.33

4c

75.18i

94.64

109.65 110.43

-20.66

4d

74.65 74.90

95.79

108.44 110.07

-21.44

complex

C-1,3

C-2

3a

74.72

96.81

3b

74.28

3c

124.56 c 124.35 126.01 124.07 125.82 124.51 c 124.00 d 123.46 124.46 125.90 126.68 123.02 123.58 125.47 c 123.87 124.29 126.25 126.59 122.81 123.74 125.26 126.09

2J CP

Cβ

Cγ

CH2

CdO

others

22.7 115.24 50.40 51.94 196.30 126.07-150.05 (m, Ph)

96.94 t

22.5 114.76 50.37 54.43 211.19 18.81 (s, CH3); 41.31 (s, CH); 127.76-149.78 (m, Ph) 97.40 t 22.6 113.92 49.72 57.63 206.18 31.41 (s, CH3); 127.41149.26 (m, Ph) 95.94 t 23.3 115.99 50.67 53.15 199.62 70.22 and 72.24 (s, CH of C5H4); 70.50 (s, C5H5); 82.31 (s, C of C5H4); 126.39-150.14 (m, Ph) 98.02 t 23.0 113.90 50.21 56.97 197.39 126.10-149.36 (m, Ph and dCH) 94.24 vt 24.3 112.16 38.92 50.51 198.86 126.76-146.84 (m, Ph)

92.73 vt 24.7 111.77 37.88 51.76 211.21 18.13 and 18.19 (s, CH3); 41.32 (s, CH); 126.00146.29 (m, Ph) 94.64 vt 24.1 111.99 38.81 55.03 206.58 31.04 (s, CH3); 127.93146.66 (m, Ph) 92.62 vt 25.7 112.03 38.13 51.21 195.68 69.46, 70.30, 71.89 and 72.11 (s, CH of C5H4); 69.90 (s, C5H5); 80.81 (s, C of C5H4); 127.25-146.58 (m, Ph)

a Spectra recorded in C D ; δ in ppm and J in Hz. Abbreviations: s, singlet; d, doublet; t, triplet; vt, virtual triplet; m, multiplet. 6 6 ∆δ(C-3a,7a) ) δ(C-3a,7a(η-indenyl complex)) - δ(C-3a,7a(sodium indenyl)), δ(C-3a,7a) for sodium indenyl 130.70 ppm. c Overlapped by Ph carbons. d 125.66 and 125.83 (s, dCH and C-4,7 or C-5,6). e d, 2JCP ) 3.5. f d, 2JCP ) 3.5. g d, 2JCP ) 7.2. h d, 2JCP ) 6.9. i Broad signal.

b

Table 3. 31P{1H} and 1H NMR Data for Cationic Vinylidene Complexes [Ru{dCdC(H)C(R1)Ph(CH2COR2)}(η5-C9H7)(PPh3)2][BF4]a 1H

η5-C9H7 complex

31P{1H}

H-1,3

H-2

JHH

H-4,5,6,7

RudCdCH

R1 ) R2 ) Ph (5a) R1 ) Ph, R2 ) iPr (5b)

36.51 s 36.56 s

5.03 d 5.07 d

6.08 t 6.09 t

2.1 2.1

5.14 m, 7.04 m 5.16 m, 7.03 m

5.73 s 5.76 s

3.16 s 2.65 s

R1 ) Ph, R2 ) Me (5c) R1 ) Ph, R2 ) Fc (5d)

36.55 s 36.28 s

5.05 d 5.05 d

5.98 t 6.04 t

1.8 1.2

5.14 m, 7.05 m 5.16 m, 7.03 m

5.45 s 5.33 s

2.48 s 2.53 s

R1 ) Ph, R2 ) (E)-CHdCHPh (5e) R1 ) H, R2 ) Ph (6a)

36.40 s

5.06 d

6.07 t

1.9

5.16 m, 7.04 m

5.58 s

2.84 s

37.96 db 40.16 db 37.98 dh 40.29 dh

5.13 br c 5.21 br i

6.25 br

c, d

4.77 de

6.34 br

i, d

4.75 dj

3.24 ddf 3.50 ddg k 3.01 ddl

38.08 dh 40.52 dh 38.36 dm 39.89 dm

5.27 br 5.62 br 5.14 br 5.59 br

6.20 br

5.75 m, d

4.52 de

2.80 m

1.09 (d, JHH ) 6.9, CH3); 1.19 (d, JHH ) 6.8, CH3); 4.21 (m, CH); 6.51-7.42 (m, Ph) 2.20 (s, CH3); 6.56-7.45 (m, Ph)

6.23 br

5.70 m, 6.85 m

n

2.99 m

4.25 (s, C5H5); 6.76-7.74 (m, Ph)

R1 ) H, R2 ) iPr (6b) R1 ) H, R2 ) Me (6c) R1 ) H, R2 ) Fc (6d)

CH2

others 6.53-7.71 (m, Ph) 0.74 (d, JHH ) 6.8, CH3); 2.20 (sept, JHH ) 6.8, CH); 6.567.53 (m, Ph) 1.67 (s, CH3); 6.51-7.52 (m, Ph) 3.72 (s, C5H5); 4.52 and 4.54 (br, C5H4); 6.44.7.51 (m, Ph) 6.33 (d, JHH ) 16.0, dCH); 6.547.53 (m, Ph and dCH) 4.37 (m, CH); 6.52-8.14 (m, Ph)

a Spectra recorded in CDCl ; δ in ppm and J in Hz. Abbreviations: s, singlet; br, broad; d, doublet; dd, doublet of doublets; t, triplet; 3 sept, septuplet; m, multiplet. b 2JPP ) 23.5. c 5.64 (m, 3H, H-1 or H-3 and H-4, H-5, H-6 or H-7). d Overlapped by Ph protons. e JHH ) 10.2. f JHH ) 17.4, JHH ) 4.5. g JHH ) 17.4, JHH ) 9.6. h 2JPP ) 23.4. i 5.67 (m, 3H, H-1 or H-3 and H-4, H-5, H-6 or H-7). j JHH ) 9.4. k 2.72 (m, 2H, CH(CH ) and CH ). l J m 2J n 3 2 2 HH ) 17.4, JHH ) 8.9. PP ) 32.1. 4.50 (m, 6H, RudCdCH, CH and C5H4).

low-field resonances, in the 13C{1H} NMR spectrum, for the RudCdCdC carbon nuclei: δ 305.06 (vt, 2JCP ) 2J CP′ ) 18.9 Hz, RudCR), 202.01 (Cβ), and 183.24 (Cγ). (b) Reactions of [Ru{dCdCdC(C9H16)}(η5-C9H7)(PPh3)2][PF6] with Enolates Derived from Methyl Ketones. The allenylidene complex 12 reacts with lithium enolates derived from acetophenone, methyl isopropyl ketone, and acetone, affording the σ-alkyn-

yl derivatives [Ru{CtCC(C9H16)(CH2COR)}(η5-C9H7)(PPh3)2] (13a-c) in 68-77% yield after chromatographic workup (Scheme 3). Formation of compounds 13a-c involves, as expected, the regioselective addition of the nucleophile at the Cγ atom of the allenylidene chain leading to the generation of a novel stereogenic center at Cγ. Enolate additions proceed in a diastereoselective manner, since only one diastereoisomer was detected

3180


Cadierno et al.

Table 4. 13C{1H} NMR Data for Cationic Vinylidene Complexes [Ru{dCdC(H)C(R1)Ph(CH2COR2)}(η5-C9H7)(PPh3)2][BF4]a η5-C9H7 C-3a,7a ∆δ(C-3a,7a)b C-4,5,6,7

RudCR

117.60

-13.10

344.41 t

98.30

117.48

-13.22

80.33

97.94

117.51

-13.19

5d

80.27

97.73

117.47

-13.23

5e

79.77

97.66

116.92

-13.78

6a

82.69d 99.82 82.87e

114.78 119.23

-13.69

6b

81.88f 99.46 82.32g

113.87 118.53

-14.50

6c

82.66 83.12

99.39

114.53 119.01

-13.93

6d

82.61 82.72

99.35

114.82 119.32

-13.63

complex

C-1,3

C-2

5a

80.45

98.09

5b

80.23

5c

123.86 c 123.70 127.23 123.72 126.27 123.70 127.31 123.16 126.67 122.65 124.71 c c 121.93 124.16 126.81 c 122.49 124.55 c c 122.44 124.62 127.29 127.38

2J CP

Cβ

Cγ

CH2

CdO

others

17.9 116.79 47.82 48.12 197.33 127.36-147.66 (m, Ph)

343.76 t

17.9 116.65 48.21 50.34 212.82 18.00 (s, CH3); 42.19 (s, CH); 127.94-147.29 (m, Ph) 343.69 t 17.6 116.58 48.01 52.02 206.23 32.36 (s, CH3); 127.65147.31 (m, Ph) 342.24 t 17.9 115.90 47.91 48.42 200.53 66.08 and 70.05 (s, CH of C5H4); 69.89 (s, C5H5); 79.93 (s, C of C5H4); 127.46-147.89 (m, Ph) 343.39 t 17.7 116.27 47.80 50.47 196.89 126.38 and 141.86 (s, dCH); 126.92-146.81 (m, Ph) 343.24 vt 16.2 116.69 35.31 48.86 199.21 127.62-144.09 (m, Ph)

342.89 vt 16.6 116.31 34.24 50.01 213.36 17.77 and 18.02 (s, CH3); 41.37 (s, CH); 127.16143.55 (m, Ph) 340.50 vt 15.2 116.67 34.26 53.24 206.89 31.12 (s, CH3); 127.30143.89 (m, Ph) 342.41 vt 15.1 116.43 35.19 50.10 202.38 69.53, 70.00, 73.43 and 73.62 (s, CH of C5H4); 70.27 (s, C5H5); 79.63 (s, C of C5H4); 128.64143.80 (m, Ph)

a Spectra recorded in CDCl ; δ in ppm and J in Hz. Abbreviations: s, singlet; d, doublet; t, triplet; vt, virtual triplet; m, multiplet. 3 ∆δ(C-3a,7a) ) δ(C-3a,7a(η-indenyl complex)) - δ(C-3a,7a(sodium indenyl)), δ(C-3a,7a) for sodium indenyl 130.70 ppm. c Overlapped by Ph carbons. d d, 2JCP ) 10.1. e d, 2JCP ) 7.9. f d, 2JCP ) 7.7. g d, 2JCP ) 7.3.

b

Table 5. IRa and 1H NMRb Data for Terminal Alkynes HCtCC(R1)Ph(CH2COR2) 1H

IR compd

ν (HCt) ν (CtC) ν (CdO)

HCt

CH2

) ) Ph (7a) R1 ) Ph, R2 ) iPr (7b)

3280 3244

2104 2111

1698 1709

2.63 s 2.66 s

4.07 s 3.52 s

R1 ) Ph, R2 ) Me (7c) R1 ) Ph, R2 ) Fc (7d) R1 ) Ph, R2 ) (E)-CHdCHPh (7e) R1 ) H, R2 ) Ph (8a)

3283 3248 3247

2118 2109 2109

1699 1667 1677

2.69 s 2.66 s 2.73 s

3.45 s 3.83 s 3.68 s

3286

2113

1683

R1 ) H, R2 ) iPr (8b)

3250

2113

1701

2.28 dc 3.37 ddd 3.62 dde 2.25 df 2.83 ddg 2.94 ddh

R1 ) H, R2 ) Me (8c)

3279

2118

1696

R1 ) H, R2 ) Fc (8d)

3301

2110

1664

R1

R2

others 7.21-7.94 (m, Ph) 1.02 (d, JHH ) 6.9, CH3); 2.57 (sept, JHH ) 6.9, CH); 7.20-7.45 (m, Ph) 2.05 (s, CH3); 7.22-7.44 (m, Ph) 4.18 (s, C5H5); 4.47 and 4.76 (br, C5H4); 7.12-7.64 (m, Ph) 6.65 (d, JHH ) 16.0, dCH); 7.21-7.52 (m, Ph and dCH)

2.26 di 2.82 ddj 3.01 ddk 2.29 dl 3.13 ddm 3.29 ddn

4.47 (ddd, JHH ) 8.0, JHH ) 6.0, JHH ) 2.3, CH); 7.24-7.97 (m, Ph) 1.02 (d, JHH ) 7.1, CH3); 1.10 (d, JHH ) 6.9, CH3); 2.53 (m, CH(CH3)2); 4.27 (ddd, JHH ) 8.7, JHH ) 6.4, JHH ) 2.5, CH); 7.25-7.43 (m, Ph) 2.15 (s, CH3); 4.21 (ddd, JHH ) 8.2, JHH ) 6.0, JHH ) 2.2, CH); 7.25-7.40 (m, Ph) 4.07 (s, C5H5); 4.46 (ddd, JHH ) 7.0, JHH ) 6.7, JHH ) 2.6, CH); 4.50 and 4.75 (br, C5H4); 7.26-7.52 (m, Ph)

a KBr; ν in cm-1. b Spectra recorded in CDCl ; δ in ppm and J in Hz. Abbreviations: s, singlet; br, broad; d, doublet; dd, doublet of 3 doublets; ddd, doublet of doublet of doublets; sept, septuplet; m, multiplet. c JHH ) 2.3. d JHH ) 17.1, JHH ) 6.0. e JHH ) 17.1, JHH ) 8.0. f J g h J i j k l HH ) 2.5. JHH ) 16.7, JHH ) 6.4. HH ) 16.7, JHH ) 8.7. JHH ) 2.2. JHH ) 16.8, JHH ) 6.0. JHH ) 16.8, JHH ) 8.2. JHH ) 2.6. m J n HH ) 17.4, JHH ) 6.7. JHH ) 17.4, JHH ) 7.0.

by NMR spectroscopy (see Tables 7 and 8).14 Since the configuration of the new chiral atom could not be elucidated from the NMR data, a single-crystal X-ray structural determination was carried out on complex 13b. An ORTEP view of the molecular geometry of this complex is shown in Figure 1. Selected bond distances and angles which are collected in the caption can be compared with those previously reported by us for other ruthenium(II) indenyl σ-alkynyl complexes [Ru(CtCR)(14) The formation of only one diastereoisomer was confirmed in the crude reaction mixture by 1H and 31P{1H} NMR spectroscopy.

(η5-C9H7)(PPh3)2]5d-f (caution must be used in the comparison of these data, due to the relative imprecision of the crystallographic determination). As expected, the structure of 13b clearly indicates that the addition of the [iPrCOCH2]- moiety takes place on the less sterically congested exo face of the allenylidene chain in [Ru{dCdCdC(C9H16)}(η5-C9H7)(PPh3)2][PF6] (12). On the basis of steric requirements, an analogous conformation is also proposed for σ-alkynyl derivatives 13a and 13c. (c) Synthesis of Vinylidene Complexes [Ru{dCdC(H)C(C9H16)(CH2COR)}(η5-C9H7)(PPh3)2]-

Additions of Enolates on Ru(II) Indenyl Allenylidenes Table 6.

13C{1H}


NMR Data for Terminal Alkynes HCtCC(R1)Ph(CH2COR2)a

compd

tCH

tC

Cγ

CH2

CdO

others

7a

74.24

87.77

47.04

49.50

195.51

7b

74.38

87.63

46.79

51.52

210.42

7c 7d

74.63 73.91

86.99 87.84

46.42 46.32

54.70 49.92

205.09 198.73

7e

75.10

87.38

47.21

53.04

196.16

8a

70.95

85.23

32.57

47.01

196.67

8b

70.72

85.19

32.45

48.63

211.09

8c 8d

70.98 70.71

84.87 85.93

32.46 32.09

51.55 48.23

205.45 200.29

127.14, 127.42, 128.41, 128.68, 128.80, and 133.33 (s, CH of Ph); 137.64 and 144.41 (s, C of Ph) 18.31 (s, CH3); 41.62 (s, CH); 127.16, 127.34, and 128.65 (s, CH of Ph); 144.36 (s, C of Ph) 31.18 (s, CH3); 126.96, 127.10, and 128.42 (s, CH of Ph); 143.66 (s, C of Ph) 69.17 and 72.07 (s, CH of C5H4); 69.69 (s, C5H5); 79.16 (s, C of C5H4); 126.68, 127.07 and 128.22 (s, CH of Ph); 144.26 (s, C of Ph) 126.29 and 142.52 (s, dCH); 127.26, 127.46, 128.59, 128.68, 129.12, and 130.65 (s, CH of Ph); 134.82 (s, C of Ph) 127.10, 127.40, 128.06, 128.55, 128.66, and 133.23 (s, CH of Ph); 136.55 and 140.52 (s, C of Ph) 17.59 and 17.65 (s, CH3); 41.17 (s, CH); 127.29, 128.58, and 133.51 (s, CH of Ph); 140.45 (s, C of Ph) 30.49 (s, CH3); 127.12, 127.25, and 128.65 (s, CH of Ph); 140.17 (s, C of Ph) 69.03, 69.24, and 72.35 (s, CH of C5H4); 69.61 (s, C5H5); 78.42 (s, C of C5H4); 127.18, 127.64, and 128.64 (s, CH of Ph); 140.83 (s, C of Ph)

a

Spectra recorded in CDCl3; δ in ppm.

Table 7.

31P{1H}

and 1H NMR Data for Neutral σ-Alkynyl Complexes [Ru{CtCC(C9H16)(CH2COR)}(η5-C9H7)(PPh3)2]a 1H

η5-C9H7h complex

31P{1H}

2J PP

H-1,3

H-2

H-4,5,6,7

CH2CdO

others

R ) Ph (13a)

52.89 d 54.44 d 53.23 d 54.29 d

34.6

4.53 br 5.07 br 4.34 br 5.20 br

5.75 br

6.03 d,b c

3.32 br

5.64 br

6.00 d,b c

2.66 de 2.79 de

5.65 br

6.00 d,f c

2.53 dg 2.67 dg

0.98, 1.52, and 2.08 (m, CH2); 1.17, 1.23, and 1.92 (s, CH3); 3.06 (m, CH); 6.62-7.98 (m, Ph) 0.80 and 1.00 (d, JHH ) 6.8, CH(CH3)2); 0.86, 1.32, and 1.72 (s, CH3); 0.93 and 1.58 (m, CH2); 1.75-2.13 (m, CH2 and CH(CH3)2); 3.14 (m, CH); 6.70-7.67 (m, Ph) 1.20, 1.23, 1.60, and 1.78 (s, CH3); 1.22, 1.70, and 2.15 (m, CH2); 3.08 (m, CH); 6.67-7.05 (m, Ph)

R ) iPr (13b) R ) Me (13c)

b

53.00 d 53.98 d

36.6 34.6

4.44 br 5.10 br

a Spectra recorded in C D ; δ in ppm and J in Hz. Abbreviations: s, singlet; br, broad; d, doublet; sept, septuplet; m, multiplet. 6 6 JHH ) 8.5. c Overlapped by Ph protons. d JHH ) 8.2. e JHH ) 18.6. f JHH ) 8.7. g JHH ) 18.3. h Legend for indenyl skeleton:

Scheme 2

[BF4] and Demetalation Reactions. Transformation of complexes 13a-c into the corresponding terminal alkynes HCtCC(C9H16)(CH2COR) (15a-c) using our synthetic methodology proceeds efficiently (see Scheme 3). Thus, in a first step the air-sensitive vinylidene derivatives [Ru{dCdC(H)C(C9H16)(CH2COR)}(η5-C9H7)(PPh3)2][BF4] (14a-c) were prepared by protonation of 13a-c with HBF4‚Et2O in diethyl ether at -20 °C (83-96% yield). Spectroscopic data of 14a-c are in agreement with the proposed structures, being comparable to those observed for the related vinylidenes 5a-e and 6a-d (see Tables 9 and 10). We note, in particular, the presence of the expected low-field carbenic CR resonance in 13C{1H} NMR spectra at ca. 328 ppm, which appears as a doublet of doublets due to the

coupling with the two diastereotopic phosphorus nuclei (2JCP ) 14.1-19.5 Hz). Remarkably, demetalation of 14a-c with acetonitrile takes place even at room temperature (ca. 30 min), giving the optically active terminal alkynes 15a-c, which have been isolated in 70-97% yield. Confirmation of the identity of 15a-c was achieved by IR and NMR spectroscopy, elemental analyses, and/or high-resolution mass spectrometry (see the Experimental Section and Tables 11 and 12). Assuming that the stereogenic Cγ atom in σ-alkynyl complexes 13a-c is not involved in the protonation and demetalation processes, an exo disposition of the ketonic fragment is also proposed for vinylidenes 14a-c and terminal alkynes 15a-c. Synthesis of Unsaturated Ruthenium(II) Cyclic Alkenyl and Carbene Complexes. Among the synthetic routes to oxacycloalkylidene complexes, those based on intramolecular nucleophilic additions of hydroxy groups at the CR of vinylidene moieties are one of the most efficient.15 It could be anticipated that the enol resonance form of the keto-substituted vinylidene complexes 5a-e, 6a-d, and 14a-c would fulfill these expectations, driving the reaction to the formation of the desired intramolecular addition products. However, these vinylidene complexes are stable in solution and (15) For a review see: Weyershausen, B.; Do¨tz, K. H. Eur. J. Inorg. Chem. 1999, 1057.

3182


Cadierno et al. Scheme 3

Table 8.

13C{1H}

NMR Data for Neutral σ-Alkynyl Complexes [Ru{CtCC(C9H16)(CH2COR)}(η5-C9H7)(PPh3)2]a η5-C9H7

complex

C-1,3

C-2

C-3a,7a ∆δ(C-3a,7a)b C-4,5,6,7 Ru-CR

2J CP

Cβ

Cγ

CH2CdO

13a

75.26 75.50 dd

97.18 110.61 111.56

-19.61

123.86 125.21 125.88 126.88

85.29 vt 22.9 114.88 54.99

48.56

13b

74.24

96.77 108.96 112.30

-20.07

122.52 124.66 125.61 127.13

84.36 vt 22.0 114.78 54.30

49.92

13c

74.06 vte 96.56 109.38 74.45 vtf 111.77

-20.12

122.83 124.92 125.28 126.16

85.02 vt 22.4 114.62 54.20

51.88

ddc

CdO

others

199.34 20.27, 28.37, and 28.48 (s, CH3); 26.81, 35.67, and 42.34 (s, CH2); 45.74 and 52.65 (s, C); 53.09 (s, CH); 127.74-140.78 (m, Ph) 212.30 18.59, 19.69, 22.95, 27.67, and 29.56 (s, CH3); 26.14, 35.10, and 41.60, (s, CH2); 41.03 (s, 44.92 and 52.06 (s, C); CH(CH3)2); 44.92 and 52.06 (s, C); 51.94 (s, CH); 127.26140.16 (m, Ph) 206.74 19.67, 27.56, 27.78, and 30.76 (s, CH3); 26.22, 35.04, and 41.56 (s, CH2); 44.91 and 52.47 (s, C); 51.88 (s, CH); 127.16140.09 (m, Ph)

a Spectra recorded in C D ; δ in ppm and J in Hz. Abbreviations: s, singlet; d, doublet; dd, doublet of doublets; vt, virtual triplet; 6 6 m, multiplet. b ∆δ(C-3a,7a) ) δ(C-3a,7a(η-indenyl complex)) - δ(C-3a,7a(sodium indenyl)), δ(C-3a,7a) for sodium indenyl 130.70 ppm. c 2J 2 d 2J e 2J 2 f 2J 2 CP ) 5.4, JCP′ ) 3.3. CP ) 6.5. CP ) JCP′ ) 2.5. CP ) JCP′ ) 5.4.

Table 9. 31P{1H} and 1H NMR Data for Cationic Vinylidene Complexes [Ru{dCdC(H)C(C9H16)(CH2COR)}(η5-C9H7)(PPh3)2][BF4]a 1H

η5-C9H7 complex

31P{1H}

2J PP

H-1,3

H-2

RudCdCH

CH2CdO

others

R ) Ph (14a)

35.23 d 37.94 d

22.8

5.59 br

6.12 br

5.26 m, b

5.12 s

2.26 dc 3.13 dc

R ) iPr (14b)

35.35 d 37.92 d

22.6

5.60 br

6.08 br

5.30 m, b

5.15 s

2.52 dd 2.71 dd

R ) Me (14c)

35.23 d 38.09 d

22.8

5.17 br 5.58 br

6.43 br

5.31 d,e 5.56 d,f b

5.05 s

1.75 dg 2.53 dg

0.39, 0.75, and 1.39 (s, CH3); 1.20, 1.64, and 1.87 (m, CH2); 2.05 (m, CH); 6.44-7.87 (m, Ph) 0.36, 0.77, and 1.30 (s, CH3); 1.09 and 1.13 (d, JHH ) 6.9, CH(CH3)2); 1.44, 1.66, and 1.96 (m, CH2); 2.15 (m, CH); 2.53 (m, CH(CH3)2); 6.48-7.51 (m, Ph) 0.32, 0.75, 1.26, and 2.12 (s, CH3); 1.18, 1.53, and 1.62 (m, CH2); 1.96 (m, CH); 6.89-7.49 (m, Ph)

b

H-4,5,6,7

a Spectra recorded in CDCl ; δ in ppm and J in Hz. Abbreviations: s, singlet; br, broad; d, doublet; sept, septuplet; m, multiplet. 3 Overlapped by Ph protons. c JHH ) 18.8. d JHH ) 19.1. e JHH ) 8.0. f JHH ) 9.4. g JHH ) 18.5.

do not undergo such cyclization processes, even in refluxing toluene. It is apparent that the electronreleasing ability of the indenyl moiety [Ru(η5-C9H7)-

(PPh3)2] decreases the electrophilic character of the vinylidene RudCR moiety, avoiding the effective cyclization reaction.16 To facilitate this process, we set out to



Table 10. 13C{1H} NMR Data for Cationic Vinylidene Complexes [Ru{dCdC(H)C(C9H16)(CH2COR)}(η5-C9H7)(PPh3)2][BF4]a η5-C9H7 complex

C-1,3

C-2

C-3a,7a ∆δ(C-3,7a)b C-4,5,6,7

RudCR

2J CP

Cβ

Cγ

CH2CdO

14a

79.96 dc 97.27 113.67 81.65 dd 119.88

-13.92

122.04 124.59 e

328.79 dd 19.5 108.87 57.49 14.6

44.53

14b

80.41 df 97.55 113.59 82.30 dg 121.07

-13.37

122.40 124.31 e

328.57 dd 18.9 109.05 59.29 14.8

46.65

14c

80.36 df 97.65 113.53 82.29 df 121.02

-13.42

122.39 125.34 e

328.25 dd 18.7 108.94 58.52 14.1

49.36

CdO

others

199.98 18.80, 26.85, and 27.02 (s, CH3); 25.27, 35.08, and 41.06 (s, CH2); 46.47 and 52.71 (s, C); 49.77 (s, CH); 127.62136.67 (m, Ph) 216.15 18.83, 19.02, 19.43, 27.63, and 27.96 (s, CH3); 26.14, 35.67, and 41.47 (s, CH2); 42.42 (s, CH(CH3)2); 46.84 and 53.11 (s, C); 50.19 (s, CH); 125.37135.91 (m, Ph) 210.28 18.91, 26.95, 27.74, and 31.38 (s, CH3); 25.99, 35.45, and 41.40 (s, CH2); 46.92 and 52.78 (s, C); 50.13 (s, CH); 128.51-147.47 (m, Ph)

a Spectra recorded in CD Cl ; δ in ppm and J in Hz. Abbreviations: s, singlet; d, doublet; dd, doublet of doublets; m, multiplet. b ∆δ(C2 2 3a,7a) ) δ(C-3a,7a(η-indenyl complex)) - δ(C-3a,7a(sodium indenyl)), δ(C-3a,7a) for sodium indenyl 130.70 ppm. c 2JCP ) 8.5. d 2JCP ) e 7.3. Overlapped by Ph carbons. f 2JCP ) 8.2. g 2JCP ) 7.7.

with HBF4 has been reported to give [Ru{dCCH2CPh2CHdC(CH3)-

were prepared. Thus, treatment of [Ru{CtCCPh2(CH2COR2)}(η5-C9H7)(PPh3)2] (R2 ) Ph (3a), iPr (3b)) with a slight excess of LiMe in tetrahydrofuran, at -20 °C, and subsequent methanolysis allows the preparation of the γ-hydroxy-alkynyl derivatives [Ru(CtCCPh2{CH2C(OH)MeR2})(η5-C9H7)(PPh3)2] (16a,b; 71% and 63% yields, respectively) (Scheme 4). We note that all attempts to promote related reactions on the corresponding vinylidene complexes 5a,b were unsuccessful, recovering instead the starting σ-alkynyl derivatives 3a,b. Complexes 16a,b have been analytically and spectroscopically characterized (see the Experimental Section). IR and 13C{1H} NMR spectra are very informative, since they show the disappearance of the typical carbonyl signals of 3a,b, confirming the reduction of the ketone group. In addition, two novel singlet resonances in the ranges δ 25.49-32.09 and 75.53-75.91 assigned to the methyl and C-OH carbon nuclei, respectively, were observed in the 13C{1H} NMR spectra. However, protonation of 16a,b does not yield the expected cyclic carbenes 17 (Scheme 5), giving instead the tetrafluoroborate salt of the diphenylallenylidene complex [Ru(dCdCdCPh2)(η5-C9H7)(PPh3)2]+ (1) in almost quantitative yields. Apparently, the protonation of the alkynyl moiety in 16a,b seems to be thermodynamically disfavored with respect to the protonation of the hydroxy function. Thus, an unstable carbocation is formed, which evolves into 1 by elimination of R-methylstyrene or 2,3dimethyl-1-butene (Scheme 5). Consequently, an alternative synthetic procedure was devised. As it is well-known, Lewis acid catalyzed intramolecular heterocyclizations of alkynes is a widely used and general method for the synthesis of unsaturated heterocycles.17 This synthetic methodology proved to be appropriate to obtain the desired cyclization products. Thus, we have found that the treatment of

O}(η5-C5H5)(CO)(PiPr3)][BF4], which is formed via an intramolecular nucleophilic addition at the electrophilic CR atom of the enol resonance form in the highly reactive vinylidene intermediate [Ru{dCdC(H)CPh2(CH2COCH3)}(η5-C5H5)(CO)(PiPr3)][BF4].2d

(17) See for example: Harding, K. E.; Tiner, T. H. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, U.K., 1991; Vol. 4, p 363.

Figure 1. ORTEP view of the structure of the σ-alkynyl complex [Ru{CtCC(C9H16)(CH2COiPr)}(η5-C9H7)(PPh3)2] (13b). Aryl groups of the triphenylphosphine ligands have been omitted for clarity. Selected bond lengths (Å) and angles (deg): Ru-C* ) 1.94(4); Ru-P1 ) 2.235(8); Ru-P2 ) 2.333(9); Ru-C1 ) 2.03(3); C1-C2 ) 1.21(3); C2-C3 ) 1.55(4); C5-O1 ) 1.18(5); C*-Ru-P1 ) 119(1); C*-Ru-P2 ) 123(1); C*-Ru-C1 ) 121(3); Ru-C1-C2 ) 173(3); C(1)-C(2)-C(3) ) 168(3). C* ) centroid of the indenyl ring (C18, C19, C20, C21, C22).

synthesize hydroxy-vinylidene complexes via reduction of the ketone group into the corresponding alcohol. Toward this aim the corresponding σ-alkynyl precursors (16) In contrast, the protonation of the analogous keto-substituted σ-alkynyl complex [Ru{CtCCPh2(CH2COCH3)}(η5-C5H5)(CO)(PiPr3)]

3184


Cadierno et al.

Table 11. IRa and 1H NMRb Data for Terminal Alkynes HCtCC(C9H16)(CH2COR) 1H

IR

c

compd

ν(HCt)

ν(CtC)

ν(CdO)

HCt

CH2

others

R ) Ph (15a)

3307

2099

1692

2.03 s

R ) iPr (15b)

3316

2104

1725

1.98 s

3.05 dc 3.16 dc 2.44 dd 2.60 dd

R ) Me (15c)

3257

2103

1718

2.00 s

0.96, 1.07, and 1.65 (s, CH3); 1.00 and 1.82 (m, CH2); 1.12-1.56 (m, CH2); 2.52 (m, CH); 7.04-7.85 (m, Ph) 0.92 and 0.94 (d, JHH ) 6.8, CH(CH3)2); 0.93 and 1.02 (s, CH3); 0.98-1.52 (m, CH3 and CH2); 2.23 (sept, JHH ) 6.8, CH(CH3)2); 2.43 (m, CH) 0.87, 0.95, 1.45, and 1.71 (s, CH3); 1.06, 1.31, and 1.50 (m, CH2); 2.38 (m, CH)

2.29 dd 2.39 dd

a KBr; ν in cm-1. b Spectra recorded in C D ; δ in ppm and J in Hz. Abbreviations: s, singlet; d, doublet; sept, septuplet; m, multiplet. 6 6 JHH ) 18.1. d JHH ) 17.9.

Table 12.

13C{1H}

NMR Data for Terminal Alkynes HCtCC(C9H16)(CH2COR)a

compd

tCH

tC

Cγ

CH2CdO

CdO

others

15a

72.72

87.49

52.92

45.23

197.06

15b

72.44

87.55

52.69

47.10

210.57

15c

72.71

87.40

52.70

49.81

204.60

18.62, 25.93, and 26.70 (s, CH3); 25.11, 34.28, and 40.99 (s, CH2); 43.97 and 49.42 (s, C); 51.32 (s, CH); 127.97, 128.60, and 132.45 (s, CH of Ph); 138.31 (s, C of Ph) 18.48, 18.51, 18.87, 25.81, and 28.68 (s, CH3); 25.09, 34.24, and 40.91 (s, CH2); 40.97 (s, CH(CH3)2), 43.69 and 49.18 (s, C); 51.16 (s, CH) 18.36, 25.95, 26.66, and 30.24 (s, CH3); 25.09, 34.07, and 40.80 (s, CH2); 43.80 and 49.20 (s, C); 51.11 (s, CH)

a

Spectra recorded in C6D6; δ in ppm.

Scheme 4

Scheme 5

σ-alkynyl complexes [Ru{CtCCPh2(CH2COR2)}(η5-C9H7)(PPh3)2] (3a,b) with ca. 5 mol % AlCl3 in dichloromethane at room temperature smoothly produces the cyclic alkenyl complexes [Ru{CdCHCPh2CHdC(R2)O}(η5-C9H7)(PPh3)2] (18a,b; 95% and 87% yields, respectively) (Scheme 6). These reactions can be monitored by IR spectroscopy, which shows the total disappearance of the typical ν(CtC) and ν(CdO) absorptions of 3a,b. In the NMR spectra, the most noticeable resonances are

(i) (1H NMR) two doublets (ca. JHH ) 2 Hz) in the range 4.74-5.57 ppm assigned to the olefinic protons of the six-membered ring and (ii) (13C{1H} NMR) a triplet signal (ca. 2JCP ) 17 Hz) at ca. 163 ppm for the Ru-CR atom18 and singlets for the dCH (δ 99.50-117.64) and dC (δ 151.42-157.67) carbons. As expected from the ability of alkenyl complexes to undergo electrophilic additions at the Cβ atom to give carbene derivatives,18,19 treatment of THF solutions of 18a,b with HBF4 at -20 °C leads to the formation of


Organometallics, Vol. 20, No. 14, 2001 3185 Scheme 6

Scheme 7

the air-stable oxacycloalkylidenes [Ru{dCCH2CPh2CHdC(R2)O}(η5-C9H7)(PPh3)2][BF4] (R2 ) Ph (19a), iPr (19b)), which have been isolated in 83 and 89% yields, respectively (Scheme 6). The presence of the carbenic moiety is clearly confirmed by the 13C{1H} NMR spectra, which show the typical low-field resonance of the carbenic carbon nuclei at ca. δ 302 (t, 2JCP ) 11.8-14.3 Hz). The spectra also show resonances assignable to the CH2 (δ 67.62-68.39), dCH (δ 109.14-115.39), dC (δ 153.48-160.68), and CPh2 (δ 43.60-44.71) carbons of the six-membered heterocyclic skeletons. To extend the scope of this synthetic route to optically active cyclic carbene complexes, we examined the behavior of the analogous chiral keto-alkynyl derivative 13a toward AlCl3. Under analogous reaction conditions, the chiral oxacycloalkenyl complex 20 was obtained and isolated (78% yield) as an air-stable solid. The subsequent protonation in THF with HBF4 at -20 °C gives the desired oxacyclocarbene complex 21 in 83% yield (Scheme 7). Since the analytical and spectroscopic data of 20 and 21 are comparable to those observed for their achiral counterparts, 18a,b and 19a,b will not be further discussed. Concluding Remarks In this work a metal-mediated synthetic approach for γ-keto-substituted alkynes HCtCCR2(CH2COR), which result from the formal coupling of 2-propyn-1-ols with methyl ketones, is reported. This methodology constitutes an alternative to the known coupling of propar(18) These chemical shifts and coupling constants are comparable to those found in related ruthenium(II) indenyl alkenyl derivatives [Ru{C(R)dC(H)R′}(η5-C9H7)L2] (L ) PPh3; L2 ) dppm): (a) Bassetti, M.; Casellato, P.; Gamasa, M. P.; Gimeno, J.; Gonza´lez-Bernardo, C.; Martıń-Vaca, B. Organometallics 1997, 16, 5470. (b) Gamasa, M. P.; Gimeno, J.; Martıń-Vaca, B. M. Organometallics 1998, 17, 3707. See also ref 5c. (19) For theoretical calculations on transition-metal alkenyl complexes see: Kostic, N. M.; Fenske, R. F. Organometallics 1982, 1, 974.

gylic alcohols with ketones containing R-hydrogens via [Co2(CO)6]-stabilized propargylium ions, which also yields γ-keto-substituted alkynes.20 The synthetic procedure is based on the electronic and/or steric ability of the fragment [Ru(η5-C9H7)(PPh3)2] to promote the following processes involved in the synthetic route. (i) Stabilization of the coordinated allenylidene groups CdCdCR2 which results from the dehydration of propargylic alcohols HCtCC(OH)R2. (ii) The regioselective addition of lithium enolates derived from methyl ketones at the Cγ atom of the allenylidene chain to give the keto-alkynyl complexes [Ru{CtCCR2(CH2COR)}(η5-C9H7)(PPh3)2] (3a-e and 4a-d). The steric protection of the electrophilic CR allows the nucleophilic addition at the more accessible Cγ atom. (iii) The elimination of the free γ-keto-substituted alkyne HCtCCR2(CH2COR) (7a-e and 8a-d) which can be efficiently achieved via selective Cβ protonation of 3a-e and 4a-d to afford vinylidene complexes [Ru{dCdC(H)CR2(CH2COR)}(η5-C9H7)(PPh3)2]+ (5a-e and 6a-d), followed by the vinylidene-π-terminal alkyne tautomerization in refluxing acetonitrile, generating the species [Ru{η2-HCtCCR2(CH2COR)}(η5-C9H7)(PPh3)2]+. The ready exchange of the coordinated alkyne for acetonitrile leads to the free alkynes and the quantitative recovery of the metal fragment as the acetonitrile complex [Ru(NtCMe)(η5-C9H7)(PPh3)2][BF4] (9). The generality of this synthetic procedure is shown by the synthesis of chiral γ-keto-alkynes 15a-c, which are obtained from the formal coupling of 2-exo-ethynyl1,3,3-trimethyl-2-endo-norbornanol (11) with methyl ketones. Thus, the synthesis of the first optically active allenylidene derivative, [Ru{dCdCdC(C9H16)}(η5-C9H7)(20) For general reviews on the synthetic utility of metal-complexed propargyl cations see: (a) Nicholas, K. M. Acc. Chem. Res. 1987, 20, 207. (b) Smit, W. A.; Caple, R.; Smoliakova, I. P. Chem. Rev. 1994, 94, 2359. (c) McGlinchey, M. J.; Girard, L.; Ruffolo, R. Coord. Chem. Rev., 1995, 143, 331. (d) Amouri, H.; Gruselle, M. Chem. Rev. 1996, 96, 1077. (e) Melikyan, G. G.; Nicholas, K. M. In Modern Acetylene Chemistry; Stang, P. J., Diederich, F., Eds.; VCH: New York, 1995.

3186


(PPh3)2][PF6] (12), is reported. This precursor has also proven to be an excellent substrate to promote regioand diastereoselective additions of enolates [CH2COR]-, allowing, therefore, the diastereoselective synthesis of the final terminal alkynes of interest as building blocks in organic synthesis. Moreover, a novel and general synthetic strategy for the preparation of unsaturated cyclic alkenyl and carbene ruthenium(II) complexes from γ-keto-alkynyl derivatives [Ru{CtCCR2(CH2COR)}(η5-C9H7)(PPh3)2] has also been described. These alkynyl species are able to undergo AlCl3-catalyzed intramolecular cyclization reactions to give oxacycloalkenyl complexes: i.e., 18a,b and 20. The subsequent protonation gives oxacyclocarbene complexes, i.e. 19a,b and 21, in high yields. Further studies concerning the scope and limitations of these processes are in progress.5e Experimental Section The manipulations were performed under an atmosphere of dry nitrogen using vacuum-line and standard Schlenk techniques. All reagents were obtained from commercial suppliers and used without further purification. Solvents were dried by standard methods and distilled under nitrogen before use. Compounds [Ru{dCdCdC(R1)Ph}(η5-C9H7)(PPh3)2][PF6] (R1 ) Ph (1), H (2)),5a [RuCl(η5-C9H7)(PPh3)2] (10),12 and 2-exoethynyl-1,3,3-trimethyl-2-endo-norbornanol (11)13 were prepared by following the methods reported in the literature. Infrared spectra were recorded on a Perkin-Elmer 1720-XFT spectrometer. The C and H analyses were carried out with a Perkin-Elmer 2400 microanalyzer. High-resolution mass spectra were recorded using a MAT-95 spectrometer. NMR spectra were recorded on a Bruker AC300 instrument at 300 MHz (1H), 121.5 MHz (31P), or 75.4 MHz (13C) using SiMe4 or 85% H3PO4 as standards. DEPT experiments have been carried out for all the compounds reported in this paper. (a) Synthesis of σ-Alkynyl Complexes [Ru{CtCC(R1)Ph(CH2COR2)}(η5-C9H7)(PPh3)2] (R1 ) Ph, R2 ) Ph (3a), iPr (3b), Me (3c), (η5-C H )Fe(η5-C H ) (3d), (E)-CHdCHPh 5 4 5 5 (3e); R1 ) H, R2 ) Ph (4a), iPr (4b), Me (4c), (η5-C5H4)Fe(η5-C5H5) (4d)). A solution of LiCH2COR2 (obtained in situ by treatment of the corresponding ketone (1 mmol) with LDA (0.179 g, 1 mmol) at -20 °C in 10 mL of THF for 30 min) was added at -20 °C to a solution of [Ru{dCdCdC(R1)Ph}(η5C9H7)(PPh3)2][PF6] (R1 ) Ph (1), H (2); 1 mmol) in 30 mL of THF. The mixture was warmed to room temperature, and the solvent was then removed in vacuo. The resulting solid residue was dissolved in dichloromethane (ca. 5 mL) and transferred to an Al2O3 (neutral; activity grade I) chromatography column. Elution with a mixture of hexane and diethyl ether (1/2) gave an orange band from which σ-alkynyl complexes 3a-e and 4a-d were isolated as orange solids after solvent removal. 3a: yield 83% (0.871 g); IR (KBr, cm-1) ν 1702 (CdO), 2075 (CtC). Anal. Calcd for RuC68H54P2O (1050.19): C, 77.77; H, 5.18. Found: C, 77.33; H, 5.19. 3b: yield 65% (0.660 g); IR (KBr, cm-1) ν 1721 (CdO), 2086 (CtC). Anal. Calcd for RuC65H56P2O (1016.17): C, 76.83; H, 5.55. Found: C, 76.29; H, 5.33. 3c: yield 63% (0.622 g); IR (KBr, cm-1) ν 1697 (Cd O), 2080 (CtC). Anal. Calcd for RuC63H52P2O (988.13): C, 76.58; H, 5.30. Found: C, 76.46; H, 5.35. 3d: yield 78% (0.903 g); IR (KBr, cm-1) ν 1679 (CdO), 2082 (CtC). Anal. Calcd for RuFeC72H58P2O (1158.11): C, 74.67; H, 5.05. Found: C, 75.27; H, 5.28. 3e: yield 81% (0.871 g); IR (KBr, cm-1) ν 1652 (Cd O), 2052 (CtC). Anal. Calcd for RuC70H56P2O (1076.23): C, 78.12; H, 5.24. Found: C, 77.91; H, 5.18. 4a: yield 62% (0.604 g); IR (KBr, cm-1) ν 1706 (CdO), 2073 (CtC). Anal. Calcd for RuC62H50P2O (974.09): C, 76.45; H, 5.17. Found: C, 76.13; H, 5.09. 4b: yield 65% (0.611 g); IR (KBr, cm-1) ν 1705 (CdO),

Cadierno et al. 2092 (CtC). Anal. Calcd for RuC59H52P2O (940.07): C, 75.38; H, 5.57. Found: C, 74.92; H, 5.48. 4c: yield 71% (0.647 g); IR (KBr, cm-1) ν 1709 (CdO), 2089 (CtC). Anal. Calcd for RuC57H48P2O (912.03): C, 75.06; H, 5.30. Found: C, 75.21; H, 5.17. 4d: yield 69% (0.746 g); IR (KBr, cm-1) ν 1658 (CdO), 2092 (CtC). Anal. Calcd for RuFeC66H54P2O (1082.01): C, 73.26; H, 5.03. Found: C, 72.91; H, 5.18. (b) Synthesis of Vinylidene Complexes [Ru{dCdC(H)C(R1)Ph(CH2COR2)}(η5-C9H7)(PPh3)2][BF4] (R1 ) Ph, R2 ) Ph (5a), iPr (5b), Me (5c), (η5-C5H4)Fe(η5-C5H5) (5d), (E)-CHdCHPh (5e); R1 ) H, R2 ) Ph (6a), iPr (6b), Me (6c), (η5-C5H4)Fe(η5-C5H5) (6d)). A diluted solution of HBF4‚ Et2O in diethyl ether was added dropwise at -20 °C to a stirred solution of the corresponding σ-alkynyl complex [Ru{CtCC(R1)Ph(CH2COR2)}(η5-C9H7)(PPh3)2] (3a-e and 4a-d; 1 mmol) in 100 mL of diethyl ether. Immediately, an insoluble solid precipitated but the addition was continued until no further solid was formed. The solution was then decanted and the brown solid washed with diethyl ether (3 × 20 mL) and vacuum-dried. 5a: yield 88% (1.001 g); IR (KBr, cm-1) ν 1065 (BF4-), 1689 (CdO). Anal. Calcd for RuC68H55F4P2BO (1138.00): C, 71.77; H, 4.87. Found: C, 71.08; H, 5.06. 5b: yield 89% (0.982 g); IR (KBr, cm-1) ν 1061 (BF4-), 1710 (Cd O). Anal. Calcd for RuC65H57F4P2BO (1103.98): C, 70.72; H, 5.20. Found: C, 69.95; H, 5.06. 5c: yield 87% (0.935 g); IR (KBr, cm-1) ν 1059 (BF4-), 1712 (CdO). Anal. Calcd for RuC63H53F4P2BO (1075.43): C, 70.33; H, 4.96. Found: C, 70.12; H, 4.81. 5d: yield 88% (1.096 g); IR (KBr, cm-1) ν 1061 (BF4-), 1660 (CdO). Anal. Calcd for RuFeC72H59F4P2BO (1245.92): C, 69.41; H, 4.77. Found: C, 69.45; H, 4.95. 5e: yield 82% (0.954 g); IR (KBr, cm-1) ν ) 1057 (BF4-), 1662 (CdO). Anal. Calcd for RuC70H57F4P2BO (1064.04): C, 72.22; H, 4.93. Found: C, 72.79; H, 4.93. 6a: yield 89% (0.945 g); IR (KBr, cm-1) ν 1058 (BF4-), 1657 (CdO). Anal. Calcd for RuC62H51F4P2BO (1061.90): C, 70.12; H, 4.84. Found: C, 70.52; H, 4.52. 6b: yield 84% (0.863 g); IR (KBr, cm-1) ν 1060 (BF4-), 1705 (CdO). Anal. Calcd for RuC59H53F4P2BO (1027.88): C, 68.94; H, 5.20. Found: C, 68.51; H, 5.23. 6c: yield 94% (0.940 g); IR (KBr, cm-1) ν 1060 (BF4-), 1712 (CdO). Anal. Calcd for RuC57H49F4P2BO (999.84): C, 68.47; H, 4.94. Found: C, 68.52; H, 4.88. 6d: yield 74% (0.866 g); IR (KBr, cm-1) ν 1061 (BF4-), 1654 (CdO). Anal. Calcd for RuFeC66H55F4P2BO (1169.82): C, 67.76; H, 4.73. Found: C, 68.02; H, 4.69. (c) Synthesis of Terminal Alkynes HCtCC(R1)Ph(CH2COR2) (R1 ) Ph, R2 ) Ph (7a), iPr (7b), Me (7c), (η5C5H4)Fe(η5-C5H5) (7d), (E)-CHdCHPh (7e); R1 ) H, R2 ) Ph (8a), iPr (8b), Me (8c), (η5-C5H4)Fe(η5-C5H5) (8d)). A solution of the corresponding vinylidene complex [Ru{dCd C(H)C(R1)Ph(CH2COR2)}(η5-C9H7)(PPh3)2][BF4] (5a-e and 6ad; 1 mmol) in acetonitrile (30 mL) was heated under reflux for 30 min. The solution was then evaporated to dryness and the resulting solid residue extracted with diethyl ether (ca. 50 mL) and filtered. A yellow solid containing mainly the nitrile complex [Ru(NtCMe)(η5-C9H7)(PPh3)2][BF4] (9) remains insoluble. The extract was evaporated to dryness and the crude product purified by column chromatography on silica gel with a mixture of hexane and diethyl ether (6/1) as eluent. Evaporation of the solvents gave terminal alkynes 7a-e and 8a-d. 7a: white solid; yield 86% (0.267 g). Anal. Calcd for C23H18O (310.94): C, 89.00; H, 5.84. Found: C, 88.91; H, 5.90. 7b: white solid; yield 80% (0.221 g). Anal. Calcd for C20H20O (276.37): C, 86.92; H, 7.29. Found: C, 86.45; H, 7.34. 7c: white solid; yield 93% (0.231 g). Anal. Calcd for C18H16O (248.32): C, 87.06; H, 6.49. Found: C, 86.91; H, 6.55. 7d: orange solid; yield 73% (0.305 g). Anal. Calcd for FeC27H22O (418.31): C, 77.52; H, 5.30. Found: C, 77.27; H, 5.48. 7e: white solid; yield 78% (0.262 g). Anal. Calcd for C25H20O (336.43): C, 89.25; H, 5.99. Found: C, 89.12; H, 6.14. 8a: white solid; yield 82% (0.192 g). Anal. Calcd for C17H14O (234.30): C, 87.14; H, 6.02. Found: C, 87.21; H, 6.12. 8b: white solid; yield 76% (0.152 g). Anal. Calcd for C14H16O (200.28): C, 83.96; H, 8.05.

Additions of Enolates on Ru(II) Indenyl Allenylidenes Found: C, 83.78; H, 8.10. 8c: colorless oil; yield 80% (0.138 g); HRMS m/z calcd for C12H12O (found) M+ ) 172.088 809 (172.088 527). 8d: orange solid; yield 72% (0.246 g). Anal. Calcd for FeC21H18O (342.22): C, 73.70; H, 5.30. Found: C, 73.60; H, 5.22. (d) Synthesis of the Allenylidene Complex [Ru{dCd CdC(C9H16)}(η5-C9H7)(PPh3)2][PF6] (12). To a solution of [RuCl(η5-C9H7)(PPh3)2] (10; 0.776 g, 1 mmol) in 50 mL of MeOH were added NaPF6 (0.336 g, 2 mmol) and 2-exo-ethynyl1,3,3-trimethyl-2-endo-norbornanol (11; 0.356 g, 2 mmol). The reaction mixture was heated under reflux for 30 min. The solvent was then removed under vacuum, the crude product extracted with CH2Cl2, and the extract filtered. Concentration of the resulting solution to ca. 5 mL followed by the addition of 50 mL of diethyl ether precipitated a red solid, which was washed with diethyl ether (2 × 20 mL) and dried in vacuo. Yield: 80% (0.837 g). IR (KBr, cm-1): ν 1963 (CdCdC), 838 (PF6-). Anal. Calcd for RuC57H53F6P3 (1046.02): C, 65.45; H, 5.10. Found: C, 64.83; H, 5.09. 31P{1H} NMR (CDCl3): δ 47.09 and 47.21 (d, 2JPP ) 23.2 Hz) ppm. 1H NMR (CDCl3): δ 1.04, 1.05, and 1.14 (s, 3H each, CH3), 1.30, 1.54, 1.62, and 1.87 (m, 1H each, CH2), 1.77 (m, 2H, CH2), 2.27 (m, 1H, CH), 5.19 (br, 2H, H-1 and H-3), 5.35 (br, 1H, H-2), 6.28 and 6.36 (d, 1H each, JHH ) 7.7 Hz, H-4, H-5, H-6 or H-7), 6.91-7.67 (m, 32H, Ph and H-4, H-5, H-6 or H-7) ppm. 13C{1H} NMR (CD2Cl2): δ 18.87, 25.19, and 26.51 (s, CH3), 25.24, 34.38, and 44.95 (s, CH2), 47.72 (s, CH), 57.57 and 64.34 (s, C), 83.52 and 84.60 (br, C-1 and C-3), 98.10 (s, C-2), 112.55 and 114.07 (s, C-3a and C-7a), 123.21, 124.09, 129.17, and 131.39 (s, C-4, C-5, C-6 and C-7), 123.21-135.27 (m, Ph), 183.24 (s, Cγ), 202.01 (s, Cβ), 305.06 (vt, 2JCP ) 2JCP′ ) 18.9 Hz, RudCR) ppm; ∆δ(C-3a,7a) ) -17.39. (e) Synthesis of σ-Alkynyl Complexes [Ru{CtCC(C9H16)(CH2COR)}(η5-C9H7)(PPh3)2] (R ) Ph (13a), iPr (13b), Me (13c)). These complexes were prepared as described for 3a-e and 4a-d by starting from the allenylidene derivative [Ru{dCdCdC(C9H16)}(η5-C9H7)(PPh3)2][PF6] (12; 1.046 g, 1 mmol) and the corresponding ketone (1 mmol). Products were purified by column chromatography on Al2O3 (neutral; activity grade I) with a mixture of hexane and diethyl ether (1/1) as eluent. Evaporation of the solvents gave complexes 13a-c as red solids. 13a: yield 77% (0.785 g); IR (KBr, cm-1) ν 2070 (CtC), 1694 (CdO). Anal. Calcd for RuC65H60P2O (1020.22): C, 76.52; H, 5.94. Found: C, 76.56; H, 6.29. 13b: yield 68% (0.670 g); IR (KBr, cm-1) ν 2070 (CtC), 1718 (CdO). Anal. Calcd for RuC62H62P2O (986.20): C, 75.51; H, 6.33. Found: C, 75.47; H, 6.60. 13c: yield 76% (0.728 g); IR (KBr, cm-1) ν 2072 (CtC), 1723 (CdO). Anal. Calcd for RuC60H58P2O (958.15): C, 75.21; H, 6.10. Found: C, 74.86; H, 6.21. (f) Synthesis of Vinylidene Complexes [Ru{dCdC(H)C(C9H16)(CH2COR)}(η5-C9H7)(PPh3)2][BF4] (R ) Ph (14a), iPr (14b), Me (14c)). These complexes were obtained as brown solids as described for 5a-e and 6a-d, starting from the corresponding σ-alkynyl complex [Ru{CtCC(C9H16)(CH2COR)}(η5-C9H7)(PPh3)2] (13a-c) (1 mmol). 14a: yield 83% (0.920 g); IR (KBr, cm-1) ν 1663 (CdO), 1060 (BF4-). 14b: yield 85% (0.913 g); IR (KBr, cm-1) ν 1702 (CdO), 1058 (BF4-). 14c: yield 96% (1.004 g); IR (KBr, cm-1) ν 1711 (CdO), 1057 (BF4-). Complexes 14a-c were too sensitive to moisture and oxygen to give satisfactory elemental analyses. (g) Synthesis of Terminal Alkynes HCtCC(C9H16)(CH2COR) (R ) Ph (15a), iPr (15b), Me (15c)). These compounds were prepared as described for 7a-e and 8a-d, starting from the corresponding vinylidene complex [Ru{dCd C(H)C(C9H16)(CH2COR)}(η5-C9H7)(PPh3)2][BF4] (14a-c; 1 mmol). 15a: white solid; yield 79% (0.221 g). Anal. Calcd for C20H24O (280.41): C, 85.67; H, 8.63. Found: C, 86.02; H, 8.84. 15b: colorless oil; yield 70% (0.172 g); HRMS m/z calcd for C20H24O (found) M+ 246.198 869 (246.198 365). 15c: white solid; yield 97% (0.212 g). Anal. Calcd for C15H22O (218.34): C, 82.51; H, 10.15. Found: C, 81.73; H, 10.34.

Organometallics, Vol. 20, No. 14, 2001 3187 (h) Synthesis of σ-Alkynyl Complexes [Ru(CtCCPh2{CH2C(OH)MeR2})(η5-C9H7)(PPh3)2] (R2 ) Ph (16a), iPr (16b)). LiMe (1.5 M in diethyl ether; 1 mL, 1.5 mmol) was added at -20 °C to a solution of the corresponding σ-alkynyl complex [Ru{CtCCPh2(CH2COR2)}(η5-C9H7)(PPh3)2] (R2 ) Ph (3a), iPr (3b); 1 mmol) in 20 mL of THF. The mixture was stirred at -20 °C for 45 min, and MeOH (5 mL) was then added. The resulting solution was warmed to room temperature, and the solvent was then removed in vacuo. The resulting solid residue was extracted with hexane (ca. 80 mL) and filtered. Evaporation of the solvent gave complexes 16a,b as orange solids. 16a: yield 71% (0.757 g); IR (KBr, cm-1) ν 2065 (CtC), 3317 (O-H); 31P{1H} NMR (C6D6) δ 50.70 and 51.91 (d, 2JPP ) 23.2 Hz) ppm; 1H NMR (C6D6) δ 1.61 (s, 3H, CH3), 3.10 and 3.17 (d, 1H each, JHH ) 13.7 Hz, CH2), 3.22 (br, 1H, OH), 4.75 and 5.16 (br, 1H each, H-1 and H-3), 5.45 (br, 1H, H-2), 6.61-8.04 (m, 49H, Ph and H-4, H-5, H-6 and H-7) ppm; 13 C{1H} NMR (C6D6) δ 32.09 (s, CH3), 50.04 (s, Cγ), 54.02 (s, CH2), 71.71 and 73.02 (s, C-1 and C-3), 75.53 (s, C-OH), 96.48 (s, C-2), 104.29 (vt, 2JCP ) 2JCP′ ) 21.6 Hz, Ru-CR), 110.48 and 110.80 (s, C-3a and C-7a), 116.18 (s, Cβ), 124.62-152.20 (m, Ph, C-4, C-5, C-6 and C-7) ppm; ∆δ(C-3a,7a) ) -20.06. Anal. Calcd for RuC69H58P2O (1066.23): C, 77.72; H, 5.48. Found: C, 78.10; H, 5.31. 16b: yield 63% (0.650 g); IR (KBr, cm-1) ν 2062 (CtC), 3332 (O-H); 31P{1H} NMR (C6D6) δ 50.30 and 52.10 (d, 2JPP ) 33.4 Hz) ppm; 1H NMR (C6D6) δ 1.08 (d, 3H, JHH ) 8.2 Hz, CH(CH3)2), 1.11 (s, 3H, CH3), 1.23 (d, 3H, JHH ) 6.7 Hz, CH(CH3)2), 1.95 (m, 1H, CH(CH3)2), 2.86 (br, 2H, CH2), 3.52 (br, 1H, OH), 4.50 and 5.25 (br, 1H each, H-1 and H-3), 5.40 (br, 1H, H-2), 6.42-7.83 (m, 44H, Ph and H-4, H-5, H-6 and H-7) ppm; 13C{1H} NMR (C6D6) δ 18.25 and 18.91 (s, CH(CH3)2), 25.49 (s, C(CH3)OH), 42.10 (s, CH(CH3)2), 47.92 (s, Cγ), 49.42 (s, CH2), 71.97 and 74.14 (s, C-1 and C-3), 75.91 (s, C-OH), 97.09 (s, C-2), 105.45 (vt, 2JCP ) 2JCP′ ) 23.4 Hz, Ru-CR), 111.30 (s, C-3a and C-7a), 115.98 (s, Cβ), 125.91152.71 (m, Ph, C-4, C-5, C-6 and C-7) ppm; ∆δ(C-3a,7a) ) -20.40. Anal. Calcd for RuC66H60P2O (1032.22): C, 76.79; H, 5.85. Found: C, 77.01; H, 5.90. (i) Synthesis of Alkenyl Complexes [Ru{CdCHCPh2CHdC(R2)O}(η5-C9H7)(PPh3)2] (R2 ) Ph (18a), iPr (18b)). A solution of the corresponding σ-alkynyl complex [Ru{Ct CCPh2(CH2COR2)}(η5-C9H7)(PPh3)2] (R2 ) Ph (3a), iPr (3b); 1 mmol) in 20 mL of dichloromethane was treated with AlCl3 (0.007 g, 0.05 mmol) at room temperature for 2 h. The solution was then evaporated to dryness and the resulting solid residue extracted with diethyl ether (ca. 100 mL) and filtered over Al2O3 (neutral; activity grade I). Evaporation of the solvent gave complexes 18a,b as yellow solids. The labeling scheme is

18a: yield 95% (0.997 g); 31P{1H} NMR (C6D6) δ 49.44 (s) ppm; NMR (C6D6) δ 4.96 (br, 2H, H-1,3), 5.25 and 5.57 (d, 1H each, JHH ) 2.4 Hz, dCH), 5.84 (m, 2H, H-4,7 or H-5,6), 5.93 (br, 1H, H-2), 6.69-7.48 (m, 47H, Ph and H-4,7 or H-5,6) ppm; 13C{1H} NMR (CD Cl ) δ 49.21 (s, C ), 74.25 (s, C-1,3), 100.94 2 2 γ (s, C-2), 106.39 and 117.64 (s, Cβ and Cδ), 113.34 (s, C-3a,7a), 123.47 and 125.57 (s, C-4,7 and C-5,6), 127.74-152.74 (m, Ph), 151.42 (s, C), 163.86 (t, 2JCP ) 16.2 Hz, Ru-CR) ppm; ∆δ(C3a,7a) ) -17.36. Anal. Calcd for RuC68H54P2O (1050.19): C, 77.77; H, 5.18. Found: C, 77.53; H, 5.07. 18b: yield 87% (0.884 g); 31P{1H} NMR (C6D6) δ 50.10 (s) ppm; 1H NMR (C6D6) δ 0.64 (d, 6H, JHH ) 6.8 Hz, CH3), 1.64 (sept, 1H, JHH ) 6.8 Hz, CH), 4.74 and 5.45 (d, 1H each, JHH ) 2.3 Hz, dCH), 4.89 (br, 2H, H-1,3), 5.73 and 6.76 (m, 2H each, H-4,7 and H-5,6), 5.86 1H

3188


(br, 1H, H-2), 6.99-7.50 (m, 40H, Ph) ppm; 13C{1H} NMR (CD2Cl2) δ 20.96 (s, CH3), 30.76 (s, CH), 48.33 (s, Cγ), 74.38 (s, C-1,3), 99.50 and 116.84 (s, Cβ and Cδ), 101.89 (s, C-2), 112.81 (s, C-3a,7a), 122.98 and 125.18 (s, C-4,7 and C-5,6), 127.45153.17 (m, Ph), 157.67 (s, C), 162.65 (t, 2JCP ) 17.0 Hz, RuCR) ppm; ∆δ(C-3a,7a) ) -17.89. Anal. Calcd for RuC65H56P2O (1016.17): C, 76.83; H, 5.55. Found: C, 77.01; H, 5.48. (j) Synthesis of Carbene Complexes [Ru{CdCCH2CHd C(R2)O}(η5-C9H7)(PPh3)2] [BF4] (R2 ) Ph (19a), iPr (19b)). To a solution of the corresponding alkenyl complex 18a,b (1 mmol) in 30 mL of THF was added dropwise, at -20 °C, an excess of a diluted solution of HBF4‚Et2O in diethyl ether (3 mmol). The resulting solution was stirred at room temperature for 30 min and then concentrated to ca. 5 mL. Addition of diethyl ether (ca. 100 mL) precipitated complexes 19a,b as brown solids, which were washed with diethyl ether (3 × 20 mL) and vacuum-dried. The labeling scheme is

19a: yield 83% (0.944 g); IR (KBr, cm-1) ν 1057 (BF4-); 31P{1H} NMR (CD2Cl2) δ 41.63 (s) ppm; 1H NMR (CD2Cl2) δ 3.79 (br, 2H, CH2), 5.05 (d, 2H, JHH ) 1.7 Hz, H-1,3), 5.30 (t, 1H, JHH ) 1.7 Hz, H-2), 5.61 (br, 1H, dCH), 6.45-7.52 (m, 49H, Ph, H-4,7 and H-5,6) ppm; 13C{1H} NMR (CD2Cl2) δ 44.71 (s, Cγ), 68.39 (s, Cβ), 77.88 (s, C-1,3), 96.35 (s, C-2), 115.39 (s, Cδ), 117.88 (s, C-3a,7a), 123.67 (s, C-4,7 or C-5,6), 127.36-144.94 (m, Ph and C-4,7 or C-5,6), 153.48 (s, C), 303.11 (t, 2JCP ) 11.8 Hz, Rud CR) ppm; ∆δ(C-3a,7a) ) -12.82. Anal. Calcd for RuC68H55F4P2BO (1138.00): C, 71.77; H, 4.87. Found: C, 72.15; H, 4.91. 19b: yield 89% (0.982 g); IR (KBr, cm-1) ν ) 1060 (BF4-); 31P{1H} NMR (CD2Cl2) δ 43.43 (s) ppm; 1H NMR (CD2Cl2) δ 0.72 (d, 6H, JHH ) 6.8 Hz, CH3), 1.89 (sept, 1H, JHH ) 6.8 Hz, CH), 3.53 (br, 2H, CH2), 4.10 (br, 1H, dCH), 5.06 (d, 2H, JHH ) 2.3 Hz, H-1,3), 5.24 (t, 1H, JHH ) 2.3 Hz, H-2), 6.72-7.47 (m, 44H, Ph, H-4,7 and H-5,6) ppm; 13C{1H} NMR (CD2Cl2) δ 21.22 (s, CH3), 30.03 (s, CH), 43.60 (s, Cγ), 67.62 (s, Cβ), 79.39 (s, C-1,3), 96.86 (s, C-2), 109.14 (s, Cδ), 117.06 (s, C-3a,7a), 123.51 (s, C-4,7 or C-5,6), 127.40-145.36 (m, Ph and C-4,7 or C-5,6), 160.68 (s, C), 301.48 (t, 2JCP ) 14.3 Hz, RudCR) ppm; ∆δ(C3a,7a) ) -13.64. Anal. Calcd for RuC65H57F4P2BO (1103.98): C, 70.72; H, 5.20. Found: C, 71.01; H, 5.12.

Cadierno et al. Table 13. Crystal Data and Structure Refinement for 13b empirical formula fw temp wavelength cryst syst space group unit cell dimens a b c R β γ V Z density (calcd) abs coeff F(000) cryst size θ range for data collecn index ranges no. of rflns collected no. of indep rflns completeness to θ ) 25.99° abs cor max and min transmissn refinement method no. of data/restraints/params goodness of fit on F2 final R indices (I > 2σ(I)) R indices (all data) absolute structure param largest diff peak and hole

RuC62H62P2O‚2CH2Cl2 1155.98 293(2) K 0.710 73 Å monoclinic P21 15.12(3) Å 11.763(10) Å 18.574(14) Å 90° 112.85(9)° 90° 3045(6) Å3 2 1.261 g cm-3 0.524 mm-1 1200 0.20 × 0.13 × 0.04 mm3 1.19-25.99° -18 e h e 18, -14 e k e 14, -22 e l e 22 13 029 11 946 (R(int) ) 0.2370) 99.8% empirical 0.978 and 0.900 full-matrix least squares on F2 11 946/1/595 0.905 R1 ) 0.1073, wR2 ) 0.2366 R1 ) 0.4440, wR2 ) 0.3977 0.1(1) 0.669 and -0.829 e Å-3

and C-3), 103.00 (s, C-2), 105.70 and 110.39 (s, Cβ and Cδ), 113.31 and 115.65 (s, C-3a and C-7a), 122.34, 123.60, 124.50, and 125.33 (s, C-4, C-5, C-6 and C-7), 126.99-138.70 (m, Ph), 151.29 (s, C), 162.79 (vt, 2JCP ) 17.0 Hz, Ru-CR) ppm; ∆δ(C3a,7a) ) -16.22. Anal. Calcd for RuC65H60P2O (1020.22): C, 76.52; H, 5.94. Found: C, 76.93; H, 5.72. (l) Synthesis of the Carbene Complex [RudCCH2C(C9H16)CHdCPhO(η5-C9H7)(PPh3)2][BF4] (21). This complex was obtained as a brown solid as described for 19a,b, starting from alkenyl complex 20 (1.02 g, 1 mmol). The labeling scheme is

(k) Synthesis of the Alkenyl Complex [Ru{CdCHC(C9H16)CHdCPhO}(η5-C9H7)(PPh3)2] (20). This complex was obtained as a yellow solid as described for 18a,b, starting from the σ-alkynyl complex [Ru{CtCC(C9H16)(CH2COPh)}(η5-C9H7)(PPh3)2] (13a) (1.02 g, 1 mmol). The labeling scheme is

Yield: 78% (0.796 g). 31P{1H} NMR (C6D6): δ 47.03 and 49.85 (d, 2JPP ) 30.5 Hz) ppm. 1H NMR (C6D6): δ 1.10, 1.18, and 1.28 (s, 3H each, CH3), 1.24 and 1.83 (m, 2H each, CH2), 1.57 and 1.96 (m, 1H each, CH2), 2.19 (m, 1H, CH), 4.90 and 5.48 (d, 1H each, JHH ) 2.3 Hz, dCH), 5.12 and 5.18 (br, 1H each, H-1 and H-3), 5.55 (m, 2H, H-4, H-5, H-6 or H-7), 6.13 (br, 1H, H-2), 6.26-6.86 (m, 37H, Ph and H-4, H-5, H-6 or H-7) ppm. 13C{1H} NMR (C6D6): δ 20.30, 25.60, and 28.69 (s, CH3), 26.81, 29.39, and 40.63 (s, CH2), 46.53, 48.80, and 53.95 (s, C and Cγ), 49.47 (s, CH), 74.40 and 74.58 (d, 2JCP ) 9.8 Hz, C-1

Yield: 83% (0.920 g). IR (KBr, cm-1): ν 1058 (BF4-). 31P{1H} NMR (CDCl3): δ 39.58 and 44.23 (br) ppm. 1H NMR (CDCl3): δ 0.68, 0.94, and 1.02 (s, 3H each, CH3), 1.19 (m, 2H, CH2), 1.46-1.69 (m, 4H, CH2), 2.32 (m, 1H, CH), 3.78 and 4.02 (br, 1H each, dCCH2), 5.00 (br, 1H, dCH), 5.20 and 5.94 (m, 1H each, H-4, H-5, H-6 or H-7), 5.31 (br, 1H, H-2), 5.48 (br, 2H, H-1 and H-3), 6.26-7.48 (m, 37H, Ph and H-4, H-5, H-6 or H-7) ppm. 13C{1H} NMR (CDCl3): δ 18.88, 24.87, and 28.11 (s, CH3), 25.99, 29.19, and 40.91 (s, CH2), 44.07, 46.01, and 52.17 (s, C and Cγ), 48.73 (s, CH), 59.81 (s, Cβ), 75.89 (br, C-1 and C-3), 95.92 (s, C-2), 113.37 (s, Cδ), 121.51 (s, C-3a and C-7a), 124.35, 125.28, and 127.42 (s, C-4, C-5, C-6 or C-7), 128.25-133.36 (m, Ph and C-4, C-5, C-6 or C-7), 151.13 (s, C), 302.45 (vt, 2JCP ) 12.5 Hz, RudCR) ppm; ∆δ(C-3a,7a) ) -9.19. Complex 21 was too sensitive to moisture and oxygen to give satisfactory elemental analyses. X-ray Diffraction. Data collection, crystal, and refinement parameters are collected in Table 13. The unit-cell parameters

Additions of Enolates on Ru(II) Indenyl Allenylidenes were obtained from the least-squares fit of 25 reflections with θ between 5 and 8°. The intensity data were measured using the ω-2θ scan technique and a variable scan rate, with a maximum scan time of 60 s per reflection. The final drift correction factors were between 0.90 and 0.98. On all reflections, profile analysis was performed.21,22 Lorentz and polarization corrections were applied, and the data were reduced to Fo2 values. The structure was solved by Patterson methods and phase expansion using the program DIRDIF23 and refined by least squares using SHELXL97.24 The hydrogen atoms were geometrically placed. During the final stages of the refinement, the positional parameters and the anisotropic thermal parameters of most of the non-H atoms were refined, except for the highly disordered carbon atoms (C6, C7, C8, C40 and C47) and the molecules of CH2Cl2, which were isotropically refined. The hydrogen atoms were isotropically refined riding with a common thermal parameter to CH2Cl2 hydrogen atoms an other to the rest. The function minimized was [∑w(Fo2 - Fc2)2/ ∑w(Fo2)2]1/2, w ) 1/[σ2(Fo2) + (0.1353P)2 + (0.0000P)] where P ) (Max(Fo2,0) + 2Fc2)/3 with σ(Fo2)2 from counting statistics. The maximum shift-to-esd ratio in the last full-matrix least(21) Grant, D. F.; Gabe, E. J. J. Appl. Crystallogr. 1978, 11, 114. (22) Lehman, M. S.; Larsen, F. K. Acta Crystallogr., Sect. A 1974, 30, 580. (23) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.; Garcıá-Granda, S.; Gould, R. O.; Smits, J. M. M.; Smykalla, C. The DIRDIF Program System; Technical Report of the Crystallographic Laboratory; University of Nijmegen, Nijmegen, The Netherlands, 1992. (24) Sheldrick, G. M. SHELX97: Programs for Crystal Structure Analysis; Institu¨t fu¨r Anorganische Chemie der Universita¨t, Tammanstrasse 4, D-3400 Go¨ttingen, Germany, 1998.

Organometallics, Vol. 20, No. 14, 2001 3189 squares cycle was 0.041. The final difference Fourier map showed no peaks higher than 0.67 e Å-3 or deeper than -0.83 e Å-3. The absolute configuration was determined with a Flack parameter of 0.1(1).25 Atomic scattering factors were taken from ref 26. Geometrical calculations were made with PARST.27 The figure showing the coordination and the atomic numbering scheme was drawn by PLATON.28 All calculations were performed at the University of Oviedo on the Scientific Computer Center and X-ray group DEC-ALPHA computers.

Acknowledgment. This work was supported by the Direccioń General de Investigacioń Cientı´fica y Tećnica (DGICYT, Project PB96-0558) and the EU (Human Capital Mobility program, Project ERBCHRXCT 940501). S.C. thanks the Ministerio de Educacioń y Cultura (MEC) for the award of a Ph.D. grant. Supporting Information Available: Crystal structure data for 13b, including tables of atomic parameters, anisotropic thermal parameters, and bond distances and bond angles. This material is available free of charge via the Internet at http://pubs.acs.org. OM010252O (25) Flack, H. D. Acta Crystallogr., Sect. A 1983, 39, 876. (26) International Tables for X-ray Crystallography; Kynoch Press: Birmingham, U.K., 1974; Vol. IV. (27) Nardelli, M. Comput. Chem. 1983, 7, 95. (28) Spek, A. L. PLATON, A Multipurpose Crystallographic Tool; University of Utrecht, Utrecht, The Netherlands, 2001.

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